Efficient surfactant system on plastic and all types of ware

ABSTRACT

Surfactant systems and compositions incorporating the same are disclosed for use as rinse aids on plastics and other wares. The surfactant systems and compositions include both liquid and solid formulations, along with methods of use for treating plastics and other wares. The surfactant systems and compositions provide synergistic combinations allowing lower actives in composition formulations of the plastic-compatible surfactant systems providing good sheeting, wetting and drying properties.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Continuation application of U.S. Ser. No. 15/157,124, filed onMay 17, 2016, which claims priority under 35 U.S.C. § 119 to provisionalapplication Ser. No. 62/163,454 filed May 19, 2015; and is also aContinuation application of U.S. Ser. No. 15/157,194, filed on May 17,2016, which claims priority under 35 U.S.C. § 119 to provisionalapplication Ser. No. 62/163,454 filed May 19, 2015, each of theseapplications are herein incorporated by reference in their entiretyincluding, without limitation, the specification, claims, and abstract,as well as any figures, tables, or drawings thereof.

FIELD OF THE INVENTION

The invention relates to surfactant systems and compositionsincorporating the same, which are particularly suitable for use as rinseaids on plastics and other wares. The invention further relates tomethods for cleaning plastics and other wares using liquid or solidcompositions incorporating the surfactant systems. In particular, theplastics-compatible surfactant systems can be used in a conventionalwarewashing machines and provide good sheeting, wetting and dryingproperties suitable for use as solutions on articles including, forexample, cookware, dishware, flatware, glasses, cups, hard surfaces,glass surfaces, vehicle surfaces, etc. The surfactant systems areparticularly effective on plastic surfaces and for use in rinse aidapplications as they outperform conventional surfactant systems employedon plastics and other wares.

BACKGROUND OF THE INVENTION

Rinsing, wetting and sheeting agents are used in a variety ofapplications to lower the surface tension of water to allow a solutionto wet surfaces more effectively. Wetting agents are included innumerous compositions including, but not limited to, cleaning solutions,antimicrobial solutions, paints, adhesives, and inks. A number ofwetting agents are currently known, each having certain advantages anddisadvantages. There is an ongoing need for improved wetting agentcompositions.

Rinsing agents are commonly used in mechanical warewashing machinesincluding dishwashers which are common in the institutional andhousehold environments. Such automatic warewashing machines clean dishesusing two or more cycles which can include initially a wash cyclefollowed by a rinse cycle, and optionally other cycles, for example, asoak cycle, a pre-wash cycle, a scrape cycle, additional wash cycles,additional rinse cycles, a sanitizing cycle, and/or a drying cycle.Rinse aids or rinsing agents are conventionally used in warewashingapplications to promote drying and to prevent the formation of spots onthe ware being washed. In order to reduce the formation of spotting,rinse aids have commonly been added to water to form an aqueous rinsethat is sprayed on the ware after cleaning is complete. A number ofrinse aids are currently known, each having certain advantages anddisadvantages. There is an ongoing need for improved rinse aidcompositions, namely those suited for use on plastic wares.

Accordingly, it is an objective of the claimed invention to developefficient surfactant systems for rinse aid applications, includingwarewashing applications for plastics and other wares.

A further object of the invention is to provide rinse aid surfactantsystems providing improved sheeting, wetting and fast drying withoutspots, particularly for plastics and other wares.

A further object of the invention is to provide a synergisticcombination of surfactants to provide the same benefits at low activelevels, including surfactant systems suitable for liquid and solidformulations which are suitable for low and high temperatureapplications.

Other objects, advantages and features of the present invention willbecome apparent from the following specification taken in conjunctionwith the accompanying drawings.

BRIEF SUMMARY OF THE INVENTION

In an embodiment, the present invention relates to surfactant systems,compositions employing the surfactant systems and methods of using thesame.

In an aspect, a surfactant system suitable for high temperatureapplications comprises at least one nonionic alcohol alkoxylateaccording to the following formulas (A or A2): R¹—O-(EO)_(x3)(PO)_(y3)—H(A), wherein R¹ is a straight-chain C₁₀-C₁₆ alkyl, wherein x₃ is from 5to 8, and wherein y₃ is from 2 to 5, or R¹—O-(EO)_(x4)(PO)_(y4)—H (A2),wherein R¹ is a straight-chain C₁₀-C₁₆ alkyl, wherein x₄ is from 4 to 6,and wherein y₄ is from 3 to 5, and a nonionic alcohol alkoxylateaccording to the following formula: R²—O-(EO)_(x1)—H (B), wherein R² isC₁₀-C₁₄ alkyl with an average of at least 2 branches per residue, andwherein x₁ is from 5 to 10. In an aspect, the high temperaturesurfactant system further comprises a nonionic alcohol alkoxylateaccording to the following formula: R²—O-(EO)_(x2)—H (C), wherein R² isC₁₀-C₁₄ alkyl with an average of at least 2 branches per residue, andwherein x₂ is from 2 to 4.

In an aspect, a surfactant system suitable for low temperatureapplications comprises at least one nonionic alcohol alkoxylateaccording to the following formulas (A or A2, B and D):R¹—O-(EO)_(x3)(PO)_(y3)—H (A), wherein R¹ is a straight-chain C₁₀-C₁₆alkyl, wherein x₃ is from 5 to 8, and wherein y₃ is from 2 to 5, orR¹—O-(EO)_(x4)(PO)_(y4)—H (A2), wherein R¹ is a straight-chain C₁₀-C₁₆alkyl, wherein x₄ is from 4 to 6, and wherein y₄ is from 3 to 5, and anonionic alcohol alkoxylate according to the following formula:R²—O-(EO)_(x1)—H (B), wherein R² is C₁₀-C₁₄ alkyl with an average of atleast 2 branches per residue, and wherein x₁ is from 5 to 10; and anonionic Guerbet alcohol alkoxylate according to the following formula:R⁷—O—(PO)y₅(EO)x₅(PO)y₆ (D), wherein R⁷ is a branched C₈-C₁₆ Guerbetalcohol, x₅ is from 5 to 30, y₅ is from 1 to 4, and y₆ is from 10 to 20.

In a further aspect, a rinse aid composition preferably suited for ahigh temperature application of use is provided comprising thesurfactant system suitable for high temperature applications comprisesat least one nonionic alcohol alkoxylate according to the formulas ofSurfactant (A or A2), a nonionic alcohol alkoxylate according to theformulas of Surfactant B, and optionally a nonionic alcohol alkoxylateaccording to the formulas of Surfactant C along with one of more of thesurfactant polymers of formulae D, E, F, G, H, I and/or J, incombination at least one additional functional ingredient. In an aspect,the foam profile of the composition has a foam height of less than 5inches after 5 minutes using the Glewwe method, and the composition isplastic-compatible providing sheeting, wetting and drying properties.Methods of use of the compositions for rinsing a surface are alsoprovided.

In a further aspect, a rinse aid composition preferably suited for a lowtemperature application of use is provided comprising the surfactantsystem suitable for low temperature applications comprises at least onenonionic alcohol alkoxylate according to the formulas of Surfactant (Aor A2), a nonionic alcohol alkoxylate according to the formulas ofSurfactant B, a Guerbet alcohol alkoxylate according to the formula ofSurfactant D along with one of more of the surfactant polymers offormulae C, E, F, G, H, I and/or J, in combination at least oneadditional functional ingredient. In an aspect, the foam profile of thecomposition has a foam height of less than 5 inches after 5 minutesusing the Glewwe method, and the composition is plastic-compatibleproviding sheeting, wetting and drying properties. Methods of use of thecompositions for rinsing a surface are also provided.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a table depicting the correlation between mean contactangle of a polypropylene substrate surface and concentration of activesrequired for complete sheeting.

FIGS. 2-3 show the results of Example 3 where various individualsurfactants were evaluated for dynamic contact angle showing wetting onvarious substrate surfaces.

FIG. 4 shows a graphical representation of the data in Tables 12-19 fromExample 5 depicting the sheeting capability of surfactant systemsaccording to embodiments of the invention.

FIGS. 5-7 show the results of Example 6 where the surfactant systemswere evaluated for dynamic contact angle showing wetting on varioussubstrate surfaces.

FIG. 8 shows the results of the 50 cycle test of Example 7 where theaverage scores for the glasses tested show benefits on sheeting anddrying using the surfactant systems according to embodiments of theinvention.

FIG. 9 shows additional results of the 50 cycle test of Example 7 wherethe redeposition protein scores for the glasses tested show benefits ofusing the surfactant systems according to embodiments of the invention.

FIG. 10 shows evaluation of surfactant systems in high temperaturewarewashing systems according to embodiments of the invention.

FIG. 11 shows evaluation of surfactant systems in low temperaturewarewashing systems according to embodiments of the invention.

FIG. 12 shows a scatterplot of glassware ratings over various time plotsat 10 locations employing a baseline conventional rinse aid and the testformulation employing a surfactant system according to embodiments ofthe invention.

Various embodiments of the present invention will be described in detailwith reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the invention. Figuresrepresented herein are not limitations to the various embodimentsaccording to the invention and are presented for exemplary illustrationof the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention relates to surfactant systems for variousapplications, including rinse aid applications and warewashingapplications for plastics and other wares. The inventive surfactantsystems have many advantages over conventional combinations ofsurfactants due to improved sheeting, wetting and fast drying,particularly for plastics and other wares.

The embodiments of this invention are not limited to particularapplications of use for the inventive surfactant systems, which can varyand are understood by skilled artisans. It is further to be understoodthat all terminology used herein is for the purpose of describingparticular embodiments only, and is not intended to be limiting in anymanner or scope. For example, as used in this specification and theappended claims, the singular forms “a,” “an” and “the” can includeplural referents unless the content clearly indicates otherwise.Further, all units, prefixes, and symbols may be denoted in its SIaccepted form.

Numeric ranges recited within the specification are inclusive of thenumbers within the defined range. Throughout this disclosure, variousaspects of this invention are presented in a range format. It should beunderstood that the description in range format is merely forconvenience and brevity and should not be construed as an inflexiblelimitation on the scope of the invention. Accordingly, the descriptionof a range should be considered to have specifically disclosed all thepossible sub-ranges as well as individual numerical values within thatrange (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

An “antiredeposition agent” refers to a compound that helps keepsuspended in water instead of redepositing onto the object beingcleaned. Antiredeposition agents are useful in the present invention toassist in reducing redepositing of the removed soil onto the surfacebeing cleaned.

As used herein, the term “cleaning” refers to a method used tofacilitate or aid in soil removal, bleaching, microbial populationreduction, and any combination thereof. As used herein, the term“microorganism” refers to any noncellular or unicellular (includingcolonial) organism. Microorganisms include all prokaryotes.Microorganisms include bacteria (including cyanobacteria), spores,lichens, fungi, protozoa, virinos, viroids, viruses, phages, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism.

As used herein, the phrase “food processing surface” refers to a surfaceof a tool, a machine, equipment, a structure, a building, or the likethat is employed as part of a food processing, preparation, or storageactivity. Examples of food processing surfaces include surfaces of foodprocessing or preparation equipment (e.g., slicing, canning, ortransport equipment, including flumes), of food processing wares (e.g.,utensils, dishware, wash ware, and bar glasses), and of floors, walls,or fixtures of structures in which food processing occurs. Foodprocessing surfaces are found and employed in food anti-spoilage aircirculation systems, aseptic packaging sanitizing, food refrigerationand cooler cleaners and sanitizers, ware washing sanitizing, blanchercleaning and sanitizing, food packaging materials, cutting boardadditives, third-sink sanitizing, beverage chillers and warmers, meatchilling or scalding waters, autodish sanitizers, sanitizing gels,cooling towers, food processing antimicrobial garment sprays, andnon-to-low-aqueous food preparation lubricants, oils, and rinseadditives.

The term “hard surface” refers to a solid, substantially non-flexiblesurface such as a counter top, tile, floor, wall, panel, window,plumbing fixture, kitchen and bathroom furniture, appliance, engine,circuit board, and dish. Hard surfaces may include for example, healthcare surfaces and food processing surfaces, instruments and the like.

As used herein, the term “phosphorus-free” or “substantiallyphosphorus-free” refers to a composition, mixture, or ingredient thatdoes not contain phosphorus or a phosphorus-containing compound or towhich phosphorus or a phosphorus-containing compound has not been added.Should phosphorus or a phosphorus-containing compound be present throughcontamination of a phosphorus-free composition, mixture, or ingredients,the amount of phosphorus shall be less than 0.5 wt-%. More preferably,the amount of phosphorus is less than 0.1 wt-%, and most preferably theamount of phosphorus is less than 0.01 wt %. Without being limitedaccording to embodiments of the invention the surfactant systems and/orcompositions employing the same may contain phosphates.

As used herein, the term “polymer” generally includes, but is notlimited to, homopolymers, copolymers, such as for example, block, graft,random and alternating copolymers, terpolymers, and higher “x”mers,further including their derivatives, combinations, and blends thereof.Furthermore, unless otherwise specifically limited, the term “polymer”shall include all possible isomeric configurations of the molecule,including, but are not limited to isotactic, syndiotactic and randomsymmetries, and combinations thereof. Furthermore, unless otherwisespecifically limited, the term “polymer” shall include all possiblegeometrical configurations of the molecule.

As used herein, the term “soil” or “stain” refers to a non-polar oilysubstance which may or may not contain particulate matter such asmineral clays, sand, natural mineral matter, carbon black, graphite,kaolin, environmental dust, etc.

As used herein, the term “substantially free” refers to compositionscompletely lacking the component or having such a small amount of thecomponent that the component does not affect the performance of thecomposition. The component may be present as an impurity or as acontaminant and shall be less than 0.5 wt-%. In another embodiment, theamount of the component is less than 0.1 wt-% and in yet anotherembodiment, the amount of component is less than 0.01 wt-%.

The term “substantially similar cleaning performance” refers generallyto achievement by a substitute cleaning product or substitute cleaningsystem of generally the same degree (or at least not a significantlylesser degree) of cleanliness or with generally the same expenditure (orat least not a significantly lesser expenditure) of effort, or both.

As used herein, the term “ware” refers to items such as eating andcooking utensils, dishes, and other hard surfaces such as showers,sinks, toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, and floors. As used herein, the term “warewashing” refers towashing, cleaning, or rinsing ware. Ware also refers to items made ofplastic. Types of plastics that can be cleaned with the compositionsaccording to the invention include but are not limited to, those thatinclude polypropylene polymers (PP), polycarbonate polymers (PC),melamine formaldehyde resins or melamine resin (melamine),acrilonitrile-butadiene-styrene polymers (ABS), and polysulfone polymers(PS). Other exemplary plastics that can be cleaned using the compoundsand compositions of the invention include polyethylene terephthalate(PET) and polystyrene polyamide.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The term “parts by weight” and variations thereof, as used herein,refers to the relative weight proportions of a substance within a totalweight of the substance in a composition.

The methods and compositions of the present invention may comprise,consist essentially of, or consist of the components and ingredients ofthe present invention as well as other ingredients described herein. Asused herein, “consisting essentially of” means that the methods andcompositions may include additional steps, components or ingredients,but only if the additional steps, components or ingredients do notmaterially alter the basic and novel characteristics of the claimedmethods and compositions.

Compositions

The compositions according to the invention include at least asurfactant system for use in cleaning plastics and other wares, alongwith a variety of other hard surfaces in need of a composition providinggood sheeting, wetting and drying properties. In some aspects, thepresent invention provides compositions that can be used as rinse aidswhich are effective at reducing spotting and filming on a variety ofsubstrates, particularly on plastic ware. In some aspects, thecompositions provide enhanced rinsing benefits at a low actives leveldue to the inventive surfactant systems employed therein. In an aspectthe compositions comprise, consist of or consist essentially of asurfactant system disclosed herein. In further aspects, the compositionsfurther include an additional nonionic surfactant and/or additionalfunctional ingredients.

Surfactant Systems

In an aspect, the surfactant system includes at least two alkoxylatesurfactants. In an aspect, the surfactant system includes at least twoalcohol alkoxylate surfactants. In an aspect, the surfactant systemincludes three alcohol alkoxylate surfactants. In further aspects, thesurfactant systems include a Guerbet alcohol surfactant. Beneficially,the combination of surfactants provides synergy such that reducedactives of the surfactants are required to provide the desiredproperties of sheeting, wetting and drying. As a further benefit, thesurfactant systems include combinations of surfactants having varyingdegrees of association, providing the beneficial result of reduced orlow foam or filming profiles, as the generation of high and/or stablefoam is not desirable according to the invention.

Exemplary ranges of the surfactants are shown in Table 1 in parts byweight of the surfactant systems.

TABLE 1 Exemplary parts by wt-ranges Surfactant 1 2 3 4 SurfactantR¹—O—(EO)_(x3)(PO)_(y3)—H 5-80 20-80 30-60 30-45 A and/or SurfactantR¹—O—(EO)_(x4)(PO)_(y4)—H 5-80 20-80 30-60 30-45 A2 SurfactantR²—O—(EO)_(x1)—H 0-80 0-60 0-50 0-40 B Surfactant R²—O—(EO)_(x2)—H 0-800-60 0-40 0-20 C Surfactant R⁷—O—(PO)y₅(EO)x₅(PO)y₆ 0-80 0-60 0-40 0-20D Surfactant R⁶—O—(PO)y₄(EO)x₄ 0-80 0-60 0-40 0-20 E (R⁶ isC₈-C₁₆-guerbet)

In an aspect, the surfactant system includes Surfactant A having thefollowing formula: R¹—O-(EO)_(x3)(PO)_(y3)—H, wherein R¹ is astraight-chain C₁₀-C₁₆-alkyl, and wherein x₃=5-8, preferably 5.5-7, andwherein y₃=2-5, preferably 2-3.5. In an aspect, the surfactant systemincludes from about 5-80 parts by weight of at least one alkoxylate ofthe formula R¹—O-(EO)_(x3)(PO)_(y3)—H, wherein R¹ is a straight-chainC₁₀-C₁₆-alkyl, and wherein x₃=5-8, preferably 5.5-7, and wherein y₃=2-5,preferably 2-3.5.

In an aspect, the surfactant system includes Surfactant A2 having thefollowing formula: R¹—O-(EO)x₄(PO)y₄-H, wherein R¹ is a straight-chainC₁₀-C₁₆-alkyl, and wherein x₄=4-8, preferably 4-5.5, and wherein y₄=2-5,preferably 3.5-5. In an aspect, the surfactant system includes fromabout 5-80 parts by weight of at least one alkoxylate of the formulaR¹—O-(EO)x₄(PO)y₄-H, wherein R¹ is a straight-chain C₁₀-C₁₆-alkyl, andwherein x₄=4-8, preferably 4-5.5, and wherein y₄=2-5, preferably 3.5-5.

In an aspect, the surfactant system includes Surfactant B has thefollowing formula: R²—O-(EO)_(x1)—H, wherein R² is a C₁₀-C₁₄ alkyl, orpreferably a C₁₂-C₁₄ alkyl, with an average at least 1 branch perresidue, or preferably at least 2 branches per residue, and whereinx₁=5-10. In an aspect, the surfactant system includes from about 0-80parts by weight of at least one alkoxylate of the formulaR²—O-(EO)_(x1)—H, where R² is a C₁₂-C₁₄ alkyl with an average at least 2branches per residue, and wherein x₁=5-10, preferably from 5-8.

In an aspect, the surfactant system includes Surfactant C having thefollowing formula: R²—O-(EO)_(x2)—H, wherein R² is a C₁₀-C₁₄ alkyl, orpreferably a C₁₂-C₁₄ alkyl with an average at least 1 branch perresidue, or preferably at least 2 branches per residue, and whereinx₂=2-4. In an aspect, the surfactant system includes from about 0-80parts by weight of at least one alkoxylate of the formulaR²—O-(EO)_(x2)—H, wherein R² is a C₁₂-C₁₄ alkyl with in average at least2 branches per residue, and wherein x₂=2-4.

In an aspect, the surfactant system includes Surfactant D having thefollowing formula: R⁷—O—(PO)y₅(EO)x₅(PO)y₆, wherein R⁷ is a C₈-C₁₆Guerbet alcohol, preferably a C₈₋₁₂ Guerbet alcohol, or more preferablya C₈-C₁₀ Guerbet alcohol, wherein x₅=5-30, preferably 9-22, whereiny₅=1-5, preferably 1-4, and wherein y₆=10-20. In an aspect, thesurfactant system includes from about 0-80 parts by weight of asurfactant R⁷—O—(PO)y₅(EO)x₅(PO)y₆, wherein R⁷ is a C8-C16 Guerbetalcohol, wherein x₅=5-30, preferably 9-22, wherein y₅=1-5, preferably1-4, and wherein y₆=10-20.

In an aspect, the surfactant system includes Surfactant E having thefollowing formula: R⁶—O—(PO)y₄(EO)x₄, wherein R⁶ is a C₈-C₁₆ Guerbetalcohol, preferably a C₈₋₁₂ Guerbet alcohol, or more preferably a C₈-C₁₀Guerbet alcohol, wherein x₄=2-10, preferably 3-8, wherein y₄=1-2. In anaspect, the surfactant system includes from about 0-80 parts by weightof a surfactant R⁶—O—(PO)y₄(EO)x₄, wherein R⁶ is a C₈-C₁₆ Guerbetalcohol, wherein x₄=2-10, preferably 3-8, wherein y₄=1-2.

In an aspect, the surfactant system comprises, consists of and/orconsists essentially:

A surfactant system including at least one of Surfactant A(R¹—O-(EO)x₃(PO)y₃-H) and/or Surfactant A2 (R¹—O-(EO)x₄(PO)y₄-H);

A surfactant system including at least one of Surfactant A(R¹—O-(EO)x₃(PO)y₃-H) and/or Surfactant A2 (R¹—O-(EO)x₄(PO)y₄-H) andSurfactant B (R²—O-(EO)_(x1)—H);

Any combinations of at least two alkoxylate surfactants of the formulasSurfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H), SurfactantC(R²—O-(EO)_(x2)—H), Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆), and/orSurfactant E (R⁶—O—(PO)y₄(EO)x₄);

Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H) and SurfactantC(R²—O-(EO)_(x2)—H);

Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H) and Surfactant D(R⁷—O—(PO)y₅(EO)x₅(PO)y₆);

Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H), SurfactantC(R²—O-(EO)_(x2)—H), and Surfactant E (R⁶—O—(PO)y₄(EO)x₄);

Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H), SurfactantC(R²—O-(EO)_(x2)—H), and Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆);

Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆) andSurfactant G (EO)x₆ (PO)y₇(EO)x₆;

Surfactant B (R²—O-(EO)_(x1)—H), Surfactant C(R²—O-(EO)_(x2)—H), andSurfactant E (R⁶—O—(PO)y₄(EO)x₄);

Surfactant B (R²—O-(EO)_(x1)—H) and/or Surfactant C(R²—O-(EO)_(x2)—H),Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆), and Surfactant E(R⁶—O—(PO)y₄(EO)x₄);

Surfactant B (R²—O-(EO)_(x1)—H) and/or Surfactant C(R²—O-(EO)_(x2)—H),and at least one of Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆), Surfactant E(R⁶—O—(PO)y₄(EO)x₄) and Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (orSurfactant A2 (R¹—O-(EO)x₄(PO)y₄-H)); and/or

Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆) and Surfactant E(R⁶—O—(PO)y₄(EO)x₄);

Surfactant B (R²—O-(EO)_(x1)—H) and Surfactant E (R⁶—O—(PO)y₄(EO)x₄);and/or

Surfactant G (EO)x₆ (PO)y₇(EO)x₆ in combination with any of the abovelisted surfactant systems. In particular aspects, a surfactant systemfor a solid rinse aid composition may preferably include Surfactant G((EO)_(x6) (PO)_(y7)(EO)_(x6)), an EO-PO-EO block copolymer, where X₆ is88-108 and Y₇ is 57-77.

In an aspect, in each of the aforementioned surfactant systems, thedesired properties of sheeting, wetting and drying are achieved throughformulations having desirable contact agent and foam profiles.

Exemplary surfactant systems are shown in Table 2 in parts by weight ofthe surfactants within the surfactant system are shown as variousembodiments as previously set forth above describing exemplarysurfactant systems. According to embodiments of the invention, thesurfactant systems shown in parts by weight of the surfactants thereof,are diluted by water and/or other process aids to provide a liquid orsolid concentrate composition. In a further aspect, the liquid or solidconcentrate compositions comprising the surfactant system are furtherdiluted to a use solution.

TABLE 2 Exemplary parts by wt-ranges Surfactant 5 6 7 8 9 10 11 12 13 1415 16 Surfactant A R¹—O—(EO)_(x3)(PO)_(y3)—H 30-50 30-45 0 0 30-45 30-4510-20 40-60 40-60 0 0  0-60 or A2 Surfactant B R²—O—(EO)_(x1)—H 20-5020-50 0 20-50 20-50 20-50 10-20 40-60 0 40-60 0 0 Surfactant CR²—O—(EO)_(x2)—H  0-40 15-40 20-50 0 15-40 0 0 0 0 0 0 0 Surfactant DR⁷—O—(PO)_(y5)(EO)_(x5)(PO)_(y6) 0 0 20-50 20-50 20-50 15-40 20-80 0 0 040-60 20-80 Surfactant E R⁶—O—(PO)_(y4)(EO)_(x4) 0 0 0 0 20-50 0 0 0 0 00 0 Surfactant G (EO)_(x6) (PO)_(y7)(EO)_(x6)  0-25  0-25  0-25  0-25 0-25  0-25  0-25 0 40-60 40-60 40-60  5-70

In an aspect, a surfactant system particularly suited for hightemperature rinse aid compositions and applications of use include thecombination of Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or SurfactantA2 (R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H) andSurfactant C(R²—O-(EO)_(x2)—H). In a further embodiment Surfactant E(R⁶—O—(PO)y₄(EO)x₄) is excluded from the high temperature rinse aidsurfactant system. In a further embodiment, for a solid compositionSurfactant G ((EO)x₆ (PO)y₇(EO)x₆), an EO-PO-EO block copolymer, isincluded.

In an embodiment, the surfactant system employing Surfactant A (orSurfactant A2)/Surfactant B are employed at a weight ratio of from about60/40 to about 40/60, or from about 50/50.

In an embodiment, the surfactant system employing Surfactant A (orSurfactant A2)/Surfactant G are employed at a weight ratio of from about60/40 to about 40/60, or from about 50/50.

In an embodiment, the surfactant system employing SurfactantB/Surfactant G are employed at a weight ratio of from about 60/40 toabout 40/60, or from about 50/50.

In an embodiment, the surfactant system employing SurfactantD/Surfactant G are employed at a weight ratio of from about 60/40 toabout 40/60, or from about 50/50.

In an embodiment, the surfactant system employing Surfactant A (orSurfactant A2)/Surfactant B/Surfactant C are employed at a weight ratioof from about 30/30/40 to about 45/45/10, or from about 35/35/30 toabout 40/40/20.

In a further aspect, a surfactant system particularly suited for lowtemperature rinse aid compositions and applications of use include thecombination of Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or SurfactantA2 (R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H) andSurfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆). In a further embodimentSurfactant E (R⁶—O—(PO)y₄(EO)x₄) is excluded from the low temperaturerinse aid surfactant system. In a further embodiment, for a solidcomposition Surfactant G ((EO)x₆ (PO)y₇(EO)x₆), an EO-PO-EO blockcopolymer, is included.

In an embodiment, the surfactant system employing Surfactant A (orSurfactant A2)/Surfactant B/Surfactant D are employed at a weight ratioof from about 30/30/40 to about 45/45/10, or from about 35/35/30 toabout 40/40/20.

In an aspect, the surfactant systems provide desirable foam profiles asmeasured according to the Glewwe method wherein after 5 minutes a foamheight of 5 inches or less is achieved, preferably less than 5 inches,more preferably 1 to 5 inches, more preferably 1 to 3 inches, and mostpreferably less than 1 inch of foam.

In an aspect, the surfactant systems reduce the contact angles of thecomposition on a substrate surface by between about 5° to about 10°, orpreferably between about 5° to about 20°, or more preferably betweenabout 10° to about 25° as compared to the contact angle of acommercially available rinse aid composition, namely a commerciallyavailable rinse aid composition not employing the surfactant systemcombination and ratio of alcohol alkoxylate surfactants. In a preferredaspect, the surfactant systems reduce the contact angles of thecomposition on a polypropylene surface by between about 5° to about 10°,or preferably between about 5° to about 20°, or more preferably betweenabout 10° to about 25° as compared to the contact angle of acommercially available rinse aid composition. Without wishing to bebound by any particular theory, it is thought that the lower the contactangle, the more a composition will induce sheeting. That is,compositions with lower contact angles will form droplets on a substratewith a larger surface area than compositions with higher contact angles.The increased surface area results in a faster drying time, with fewerspots formed on the substrate.

FIG. 1 shows a bivariate fit of the mean contact angle (degrees)measured on polypropylene (60 ppm, 80° C.) demonstrating theconcentration of sheeting agent (ppm) required for complete sheeting onthe surface decreases as there is a reduction in the contact angle ofthe rinse aid composition. Commercial rinse aids are shown in comparisonto various alcohol alkoxylate(s) surfactant systems according toembodiments of the invention. As shown, there is a linear fit to thereduction in contact angle of the surfactant system composition or therinse aid composition employing the surfactant system in comparison to acommercial rinse aid and the reduction in concentration of sheetingagent, illustrating the significant benefit of the invention inproviding surfactant systems having a reduced contact angle of betweenabout 5° to about 10°, or preferably between about 5° to about 20°, ormore preferably between about 10° to about 25° as compared to thecontact angle of a commercially available rinse aid composition, namelya commercially available rinse aid composition that does not employ thesurfactant systems according to embodiments of the invention, while alsobeing able to provide such complete sheeting at a low actives level. Insome aspects, 125 ppm or less of the surfactant system actives arerequired for complete sheeting, or 100 ppm or less, or 50 ppm or less.

In some embodiments, the alcohol alkoxylate surfactants of thesurfactant systems are selected to have certain environmentally friendlycharacteristics so they are suitable for use in food service industriesand/or the like. For example, the particular alcohol alkoxylatesurfactants may meet environmental or food service regulatoryrequirements, for example, biodegradability requirements.

In an aspect, the surfactant systems and compositions employing thesurfactant systems unexpectedly provide efficacy at lower doses, namelyuse concentrations of about 125 ppm or less of the surfactant systemactives, or 100 ppm or less, or 50 ppm or less, due to the synergy ofthe systems. In an aspect, an actives concentration of less than about5% provides effective performance. The surfactant system allows dosingat lower actives level while providing at least substantially similarperformance, as set forth in further detail in the Examples.

Additional Nonionic Surfactants

In some embodiments, the compositions of the present invention includean additional surfactant combined with the surfactant systems.Surfactants suitable for use with the compositions of the presentinvention include, but are not limited to, nonionic surfactants. In someembodiments, the surfactant systems of the present invention includeabout 1 parts by wt o about 75 parts by wt of an additional surfactant.In other embodiments the compositions of the present invention includeabout 5 parts by wt to about 50 parts by wt of an additional surfactant.In still yet other embodiments, the compositions of the presentinvention include about 10 parts by wt to about 50 parts by wt of anadditional surfactant.

In some embodiments, the rinse aid compositions employing the surfactantsystem of the present invention include about 1 wt-% to about 75 wt-% ofan additional surfactant. In other embodiments the compositions of thepresent invention include about 5 wt-% to about 50 wt-% of an additionalsurfactant. In still yet other embodiments, the compositions of thepresent invention include about 10 wt-% to about 50 wt-% of anadditional surfactant.

Useful nonionic surfactants are generally characterized by the presenceof an organic hydrophobic group and an organic hydrophilic group and aretypically produced by the condensation of an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilicalkaline oxide moiety which in common practice is ethylene oxide or apolyhydration product thereof, polyethylene glycol. Practically anyhydrophobic compound having a hydroxyl, carboxyl, amino, or amido groupwith a reactive hydrogen atom can be condensed with ethylene oxide, orits polyhydration adducts, or its mixtures with alkoxylenes such aspropylene oxide to form a nonionic surface-active agent. The length ofthe hydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield a waterdispersible or water soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic properties. Useful nonionicsurfactants include:

Block polyoxypropylene-polyoxyethylene polymeric compounds based uponpropylene glycol, ethylene glycol, glycerol, trimethylolpropane, andethylenediamine as the initiator reactive hydrogen compound (1).Examples of polymeric compounds made from a sequential propoxylation andethoxylation of initiator are commercially available from BASF Corp. Oneclass of compounds is difunctional (two reactive hydrogens) compoundsformed by condensing ethylene oxide with a hydrophobic base formed bythe addition of propylene oxide to the two hydroxyl groups of propyleneglycol. This hydrophobic portion of the molecule weighs from about 1,000to about 4,000. Ethylene oxide is then added to sandwich this hydrophobebetween hydrophilic groups, controlled by length to constitute fromabout 10% by weight to about 80% by weight of the final molecule.Another class of compounds are tetra-flinctional block copolymersderived from the sequential addition of propylene oxide and ethyleneoxide to ethylenediamine. The molecular weight of the propylene oxidehydrotype ranges from about 500 to about 7,000; and, the hydrophile,ethylene oxide, is added to constitute from about 10% by weight to about80% by weight of the molecule.

Condensation products of one mole of alkyl phenol wherein the alkylchain, of straight chain or branched chain configuration, or of singleor dual alkyl constituent, contains from about 8 to about 18 carbonatoms with from about 3 to about 50 moles of ethylene oxide (2). Thealkyl group can, for example, be represented by diisobutylene, di-amyl,polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactantscan be polyethylene, polypropylene, and polybutylene oxide condensatesof alkyl phenols. Examples of commercial compounds of this chemistry areavailable on the market under the trade names Igepal® manufactured byRhone-Poulenc and Triton′ manufactured by Union Carbide.

Condensation products of one mole of a saturated or unsaturated,straight or branched chain alcohol having from about 6 to about 24carbon atoms with from about 3 to about 50 moles of ethylene oxide (3).The alcohol moiety can consist of mixtures of alcohols in the abovedelineated carbon range or it can consist of an alcohol having aspecific number of carbon atoms within this range. Examples of likecommercial surfactant are available under the trade names Lutensol™,Dehydol™ manufactured by BASF, Neodol™ manufactured by Shell ChemicalCo. and Alfonic™ manufactured by Vista Chemical Co.

Condensation products of one mole of saturated or unsaturated, straightor branched chain carboxylic acid having from about 8 to about 18 carbonatoms with from about 6 to about 50 moles of ethylene oxide (4). Theacid moiety can consist of mixtures of acids in the above defined carbonatoms range or it can consist of an acid having a specific number ofcarbon atoms within the range. Examples of commercial compounds of thischemistry are available on the market under the trade names Disponil orAgnique manufactured by BASF and Lipopeg™ manufactured by LipoChemicals, Inc.

In addition to ethoxylated carboxylic acids, commonly calledpolyethylene glycol esters, other alkanoic acid esters formed byreaction with glycerides, glycerin, and polyhydric (saccharide orsorbitan/sorbitol) alcohols have application in this invention forspecialized embodiments, particularly indirect food additiveapplications. All of these ester moieties have one or more reactivehydrogen sites on their molecule which can undergo further acylation orethylene oxide (alkoxide) addition to control the hydrophilicity ofthese substances. Care must be exercised when adding these fatty esteror acylated carbohydrates to compositions of the present inventioncontaining amylase and/or lipase enzymes because of potentialincompatibility.

Examples of nonionic low foaming surfactants include:

Compounds from (1) which are modified, essentially reversed, by addingethylene oxide to ethylene glycol to provide a hydrophile of designatedmolecular weight; and, then adding propylene oxide to obtain hydrophobicblocks on the outside (ends) of the molecule. The hydrophobic portion ofthe molecule weighs from about 1,000 to about 3,100 with the centralhydrophile including 10% by weight to about 80% by weight of the finalmolecule. These reverse Pluronics' are manufactured by BASF Corporationunder the trade name Pluronic™ R surfactants. Likewise, the Tetronic′ Rsurfactants are produced by BASF Corporation by the sequential additionof ethylene oxide and propylene oxide to ethylenediamine. Thehydrophobic portion of the molecule weighs from about 2,100 to about6,700 with the central hydrophile including 10% by weight to 80% byweight of the final molecule.

Compounds from groups (1), (2), (3) and (4) which are modified by“capping” or “end blocking” the terminal hydroxy group or groups (ofmulti-functional moieties) to reduce foaming by reaction with a smallhydrophobic molecule such as propylene oxide, butylene oxide, benzylchloride; and, short chain fatty acids, alcohols or alkyl halidescontaining from 1 to about 5 carbon atoms; and mixtures thereof. Alsoincluded are reactants such as thionyl chloride which convert terminalhydroxy groups to a chloride group. Such modifications to the terminalhydroxy group may lead to all-block, block-heteric, heteric-block orall-heteric nonionics.

Additional examples of effective low foaming nonionics include:

The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486 issuedSep. 8, 1959 to Brown et al. and represented by the formula

in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylenechain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is aninteger of 1 to 10.

The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issuedAug. 7, 1962 to Martin et al. having alternating hydrophilic oxyethylenechains and hydrophobic oxypropylene chains where the weight of theterminal hydrophobic chains, the weight of the middle hydrophobic unitand the weight of the linking hydrophilic units each represent aboutone-third of the condensate.

The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178issued May 7, 1968 to Lissant et al. having the general formulaZ[(OR)_(n)OH]_(z) wherein Z is alkoxylatable material, R is a radicalderived from an alkylene oxide which can be ethylene and propylene and nis an integer from, for example, 10 to 2,000 or more and z is an integerdetermined by the number of reactive oxyalkylatable groups.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,677,700, issued May 4, 1954 to Jackson et al. corresponding to theformula Y(C₃H₆₀)_(n)(C₂H₄O)_(m)H wherein Y is the residue of organiccompound having from about 1 to 6 carbon atoms and one reactive hydrogenatom, n has an average value of at least about 6.4, as determined byhydroxyl number and m has a value such that the oxyethylene portionconstitutes about 10% to about 90% by weight of the molecule.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the formulaY[(C₃H₆O_(n)(C₂H₄O)_(m)H]_(x) wherein Y is the residue of an organiccompound having from about 2 to 6 carbon atoms and containing x reactivehydrogen atoms in which x has a value of at least about 2, n has a valuesuch that the molecular weight of the polyoxypropylene hydrophobic baseis at least about 900 and m has value such that the oxyethylene contentof the molecule is from about 10% to about 90% by weight. Compoundsfalling within the scope of the definition for Y include, for example,propylene glycol, glycerine, pentaerythritol, trimethylolpropane,ethylenediamine and the like. The oxypropylene chains optionally, butadvantageously, contain small amounts of ethylene oxide and theoxyethylene chains also optionally, but advantageously, contain smallamounts of propylene oxide.

Additional conjugated polyoxyalkylene surface-active agents which areadvantageously used in the compositions of this invention correspond tothe formula: P[(C₃H₆O)_(n)(C₂H₄O)_(m)H]_(x) wherein P is the residue ofan organic compound having from about 8 to 18 carbon atoms andcontaining x reactive hydrogen atoms in which x has a value of 1 or 2, nhas a value such that the molecular weight of the polyoxyethyleneportion is at least about 44 and m has a value such that theoxypropylene content of the molecule is from about 10% to about 90% byweight. In either case the oxypropylene chains may contain optionally,but advantageously, small amounts of ethylene oxide and the oxyethylenechains may contain also optionally, but advantageously, small amounts ofpropylene oxide.

Polyhydroxy fatty acid amide surfactants suitable for use in the presentcompositions include those having the structural formula R₂CON_(R1)Z inwhich: R1 is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl,ethoxy, propoxy group, or a mixture thereof; R₂ is a C₅-C₃₁ hydrocarbyl,which can be straight-chain; and Z is a polyhydroxyhydrocarbyl having alinear hydrocarbyl chain with at least 3 hydroxyls directly connected tothe chain, or an alkoxylated derivative (preferably ethoxylated orpropoxylated) thereof. Z can be derived from a reducing sugar in areductive amination reaction; such as a glycityl moiety.

The alkyl ethoxylate condensation products of aliphatic alcohols withfrom about 0 to about 25 moles of ethylene oxide are suitable for use inthe present compositions. The alkyl chain of the aliphatic alcohol caneither be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms.

The ethoxylated C₆-C₁₈ fatty alcohols and C₆-C₁₈ mixed ethoxylated andpropoxylated fatty alcohols are suitable surfactants for use in thepresent compositions, particularly those that are water soluble.Suitable ethoxylated fatty alcohols include the C₆-C₁₈ ethoxylated fattyalcohols with a degree of ethoxylation of from 3 to 50.

Suitable nonionic alkylpolysaccharide surfactants, particularly for usein the present compositions include those disclosed in U.S. Pat. No.4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include ahydrophobic group containing from about 6 to about 30 carbon atoms and apolysaccharide, e.g., a polyglycoside, hydrophilic group containing fromabout 1.3 to about 10 saccharide units. Any reducing saccharidecontaining 5 or 6 carbon atoms can be used, e.g., glucose, galactose andgalactosyl moieties can be substituted for the glucosyl moieties.(Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.positions thus giving a glucose or galactose as opposed to a glucosideor galactoside.) The intersaccharide bonds can be, e.g., between the oneposition of the additional saccharide units and the 2-, 3-, 4-, and/or6-positions on the preceding saccharide units.

Fatty acid amide surfactants suitable for use the present compositionsinclude those having the formula: R₆CON(R₇)₂ in which R₆ is an alkylgroup containing from 7 to 21 carbon atoms and each R₇ is independentlyhydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, or —(C₂H₄O)xH, where x is inthe range of from 1 to 3.

A useful class of non-ionic surfactants includes the class defined asalkoxylated amines or, most particularly, alcoholalkoxylated/aminated/alkoxylated surfactants. These non-ionicsurfactants may be at least in part represented by the general formulae:R²⁰—(PO)sN-(EO)_(t)H, R²⁰—(PO)sN-(EO)_(t)H(EO)_(t)H, and R²⁰—N(EO)_(t)H;in which R²⁰ is an alkyl, alkenyl or other aliphatic group, or analkyl-aryl group of from 8 to 20, preferably 12 to 14 carbon atoms, EOis oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2-5, t is1-10, preferably 2-5, and u is 1-10, preferably 2-5. Other variations onthe scope of these compounds may be represented by the alternativeformula: R²⁰—(PO)v-N[(EO)_(w)H][(EO)_(z)H] in which R²⁰ is as definedabove, v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2)), and w and zare independently 1-10, preferably 2-5. These compounds are representedcommercially by a line of products sold by Huntsman Chemicals asnonionic surfactants. A preferred chemical of this class includesSurfonic PEA 25 Amine Alkoxylate. Preferred nonionic surfactants for thecompositions of the invention include alcohol alkoxylates, EO/PO blockcopolymers, alkylphenol alkoxylates, and the like.

The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 ofthe Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is anexcellent reference on the wide variety of nonionic compounds generallyemployed in the practice of the present invention. A typical listing ofnonionic classes, and species of these surfactants, is given in U.S.Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975.Further examples are given in “Surface Active Agents and detergents”(Vol. I and II by Schwartz, Perry and Berch).

Additional Polymer Surfactants

As set forth regarding additional nonionic surfactants which may beincluded in compositions containing the inventive surfactant systems.Exemplary additional polymer surfactants preferred for use with thesurfactant systems according to the invention are set forth in Table 3.

TABLE 3 Surfactant Polymer Surfactant F

Where x = 12-20 y = 120-220 z = 12-20 G

Where x = 88-108 y = 57-77 z = 88-108 H

Where x = 15-25 y = 10-25 z = 15-25 I R⁴—O—(EO)_(x)(XO)_(y)—H Where R4 =C13-C15 alkyl x = 8-10 y = 1-3 and XO = Butylene oxide JR⁵—O—(EO)_(x)(PO)_(y)—H Where R5 = C12-15 alkyl x = 3-5 y = 5-7

In an aspect, the surfactant system comprises, consists of and/orconsists essentially:

Any combinations of at least two alkoxylate surfactants of the formulasSurfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H), SurfactantC(R²—O-(EO)_(x2)—H), Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆), SurfactantE (R⁶—O—(PO)y₄(EO)x₄), and/or at least one polymer surfactant selectedfrom the group consisting of Surfactants F, G, H, I, J and/orcombinations of the same;

Any combinations of at least two alkoxylate surfactants of the formulasSurfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H), SurfactantC(R²—O-(EO)_(x2)—H), Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆), and/orSurfactant E (R⁶—O—(PO)y₄(EO)x₄), and optionally at least one polymersurfactant selected from the group consisting of Surfactants F, G, H, I,J and/or combinations of the same;

Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H) and SurfactantC(R²—O-(EO)_(x2)—H), and optionally at least one polymer surfactantselected from the group consisting of Surfactants F, G, H, I, J and/orcombinations of the same;

Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H) and Surfactant D(R⁷—O—(PO)y₅(EO)x₅(PO)y₆), and optionally at least one polymersurfactant selected from the group consisting of Surfactants F, G, H, I,J and/or combinations of the same;

Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H), SurfactantC(R²—O-(EO)_(x2)—H), and Surfactant E (R⁶—O—(PO)y₄(EO)x₄), andoptionally at least one polymer surfactant selected from the groupconsisting of Surfactants F, G, H, I, J and/or combinations of the same;

Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2(R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H), SurfactantC(R²—O-(EO)_(x2)—H), and Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆), andoptionally at least one polymer surfactant selected from the groupconsisting of Surfactants F, G, H, I, J and/or combinations of the same;

Surfactant B (R²—O-(EO)_(x1)—H), Surfactant C(R²—O-(EO)_(x2)—H), andSurfactant E (R⁶—O—(PO)y₄(EO)x₄), and optionally at least one polymersurfactant selected from the group consisting of Surfactants F, G, H, I,J and/or combinations of the same;

Surfactant B (R²—O-(EO)_(x1)—H) and/or Surfactant C(R²—O-(EO)_(x2)—H),Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆), and Surfactant E(R⁶—O—(PO)y₄(EO)x₄), and optionally at least one polymer surfactantselected from the group consisting of Surfactants F, G, H, I, J and/orcombinations of the same;

Surfactant B (R²—O-(EO)_(x1)—H) and/or Surfactant C(R²—O-(EO)_(x2)—H),and at least one of Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆), Surfactant E(R⁶—O—(PO)y₄(EO)x₄) and Surfactant A (R¹—O-(EO)x₃(PO)_(y3)—H) (orSurfactant A2 (R¹—O-(EO)x₄(PO)y₄-H)), and optionally at least onepolymer surfactant selected from the group consisting of Surfactants F,G, H, I, J and/or combinations of the same;

Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆) and Surfactant E(R⁶—O—(PO)y₄(EO)x₄), and optionally at least one polymer surfactantselected from the group consisting of Surfactants F, G, H, I, J and/orcombinations of the same;

Surfactant B (R²—O-(EO)_(x1)—H) and Surfactant E (R⁶—O—(PO)y₄(EO)x₄),and optionally at least one polymer surfactant selected from the groupconsisting of Surfactants F, G, H, I, J and/or combinations of the same.

In an aspect, in each of the aforementioned surfactant systems, thedesired properties of sheeting, wetting and drying are achieved throughformulations having desirable contact agent and foam profiles.

Surfactant Systems and Compositions Employing Surfactant Systems

Typically, the surfactant systems and compositions employing surfactantsystems are formulated into liquid or solid formulations. The surfactantsystems and compositions are formulated to include components that aresuitable for use in food service industries, e.g., GRAS ingredients, apartial listing is available at 21 CFR 184. In some embodiments, thesurfactant systems and compositions are formulated to include only GRASingredients. In other embodiments, the surfactant systems andcompositions are formulated to include GRAS and biodegradableingredients.

The surfactant systems and compositions employing the surfactant systemsin a use solution preferably have a pH of 8.5 or below, 8.3 or below, or7 or below.

The surfactant systems and compositions employing the surfactant systemsin a use solution preferably have a concentration of about 125 ppm orless of the surfactant system actives, or 100 ppm or less, or 50 ppm orless, due to the synergy of the systems according to the benefits of theinvention. The surfactant systems and compositions employing thesurfactant systems allow dosing at lower actives level while providingat least substantially similar performance. In an aspect, a rinse aidcomposition employing the surfactant system particularly suited for hightemperature applications includes a surfactant system comprising acombination of Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (or SurfactantA2 (R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H) andoptionally Surfactant C(R²—O-(EO)_(x2)—H). In an embodiment, thesurfactant system employing Surfactant A (or Surfactant A2)/Surfactant Bare employed at a weight ratio of from about 60/40 to about 40/60, orfrom about 50/50. In an embodiment, the surfactant system employingSurfactant A (or Surfactant A2)/Surfactant B/Surfactant C are employedat a weight ratio of from about 30/30/40 to about 45/45/10, or fromabout 35/35/30 to about 40/40/20.

In a further embodiment Surfactant E (R⁶—O—(PO)y₄(EO)x₄) is excludedfrom the high temperature rinse aid surfactant system. In a furtherembodiment, for a solid composition Surfactant G ((EO)x₆ (PO)y₇(EO)x₆),an EO-PO-EO block copolymer, is included. Each of the additionalembodiments of the surfactant systems may further be employed for therinse aid compositions.

In an aspect, a rinse aid composition employing the surfactant systemparticularly suited for low temperature rinse aid applications includesa surfactant system comprising a combination of Surfactant A(R¹—O-(EO)_(x3)(PO)_(y3)—H) (or Surfactant A2 (R¹—O-(EO)x₄(PO)y₄-H)),Surfactant B (R²—O-(EO)_(x1)—H) and Surfactant D(R⁷—O—(PO)y₅(EO)x₅(PO)y₆). In an embodiment, the surfactant systememploying Surfactant A (or Surfactant A2)/Surfactant B/Surfactant D areemployed at a weight ratio of from about 30/30/40 to about 45/45/10, orfrom about 35/35/30 to about 40/40/20.

In a further embodiment Surfactant E (R⁶—O—(PO)y₄(EO)x₄) is excludedfrom the low temperature rinse aid surfactant system. In a furtherembodiment, for a solid composition Surfactant G ((EO)_(x6)(PO)_(y7)(EO)_(x6)), an EO-PO-EO block copolymer, is included.

In each aspect of the rinse aid compositions at least one additionalfunctional ingredient is included with the surfactant system. Thecombination of the surfactant system and the additional functionalingredient(s) provides a foam profile of the composition having a foamheight of less than 5 inches after 5 minutes using the Glewwe method. Ina further aspect, the combination of the surfactant system and theadditional functional ingredient(s) is plastic-compatible providingsheeting, wetting and drying properties which at at least equivalent orsuperior to a commercially available rinse aid composition at a lowerppm actives of the surfactant system.

Additional Functional Ingredients

The components of the surfactant system composition can further becombined with various functional components suitable for use in rinseaid applications, ware wash applications, and other applicationsrequiring sheeting, wetting, and fast drying of surfaces. In someembodiments, the surfactant system composition including the surfactantsystem and additional nonionic surfactant make up a large amount, oreven substantially all of the total weight of the composition. Forexample, in some embodiments few or no additional functional ingredientsare disposed therein. In other embodiments, additional functionalingredients may be included in the compositions to provide desiredproperties and functionalities to the compositions. For the purpose ofthis application, the term “functional ingredient” includes a materialthat when dispersed or dissolved in a use and/or concentrate solution,such as an aqueous solution, provides a beneficial property in aparticular use. Some particular examples of functional materials arediscussed in more detail below, although the particular materialsdiscussed are given by way of example only, and that a broad variety ofother functional ingredients may be used. For example, many of thefunctional materials discussed below relate to materials used in rinsingand cleaning applications. However, other embodiments may includefunctional ingredients for use in other applications.

In some embodiments, the compositions do not include a defoaming agent.In other embodiments, the compositions include less than about 30 wt-%,or less than about 20 wt-% defoaming surfactant or defoaming agent, orless than about 10 wt-% defoaming surfactant or defoaming agent, orpreferably less than about 5 wt-% defoaming surfactant or defoamingagent to provide an effective amount of defoamer component configuredfor reducing the stability of foam that may be created by the surfactantsystem. Exemplary defoaming agents include for example nonionic EOcontaining surfactants that are hydrophilic and water soluble atrelatively low temperatures, for example, temperatures below thetemperatures at which the rinse aid will be used. Without being limitedto a particular mechanism of action the inclusion of a detergentdefoaming agent may negatively interact with the surfactant system asincreasing amounts of defoamer demonstrate an antagonist effect ofdiminished efficacy due to interference with wetting and sheeting in thesurfactant systems according to the invention.

In other embodiments, the compositions may include carriers, waterconditioning agents including rinse aid polymers, binding agents forsolidification, anti-redeposition agents, antimicrobial agents,bleaching agents and/or activators, solubility modifiers, dispersants,rinse aids, metal protecting agents, stabilizing agents, corrosioninhibitors, sequestrants and/or chelating agents, builders, fragrancesand/or dyes, humectants, rheology modifiers or thickeners, hardeningagents, solidification agents, hydrotropes or couplers, buffers,solvents, pH buffers, cleaning enzymes, carriers, processing aids,solvents for liquid formulations, or others, and the like.

In an exemplary embodiment, a solid rinse aid composition according tothe invention comprises from about 10 wt-% to about 80 wt-% surfactantsystem, from about 10 wt-% to about 80 wt-% solidification aid, fromabout 0 wt-% to about 10 wt-% water conditioning agent, from about 0wt-% to about 10 wt-% chelant, from about 0 wt-% to about 20 wt-%acidulant, from about 0 wt-% to about 5 wt-% water, and from about 0wt-% to about 2 wt-% preservative and/or dye.

In a further exemplary embodiment of a solid rinse aid compositionaccording to the invention comprises from about 10 wt-% to about 65 wt-%surfactant system, from about 20 wt-% to about 60 wt-% solidificationaid, from about 0 wt-% to about 8 wt-% water conditioning agent, fromabout 0 wt-% to about 5 wt-% chelant, from about 0 wt-% to about 15 wt-%acidulant, from about 0 wt-% to about 5 wt-% water, and from about 0wt-% to about 2 wt-% preservative and/or dye.

In a still further exemplary embodiment of a solid rinse aid compositionaccording to the invention comprises from about 5 wt-% to about 30 wt-%surfactant system, from about 25 wt-% to about 65 wt-% solidificationaid, from about 0 wt-% to about 5 wt-% water conditioning agent, fromabout 0 wt-% to about 3 wt-% chelant, from about 0 wt-% to about 10 wt-%acidulant, from about 0 wt-% to about 5 wt-% water, and from about 0wt-% to about 2 wt-% preservative and/or dye.

In a still further exemplary embodiment, a liquid rinse aid compositionaccording to the invention comprises from about 2 wt-% to about 90 wt-%surfactant system, from about 0 wt-% to about 40 wt-% coupling agent,from about 0 wt-% to about 10 wt-% water conditioning agent, from about0 wt-% to about 10 wt-% chelant, from about 0 wt-% to about 15 wt-%acidulant, from about 0 wt-% to about 95 wt-% water, and from about 0wt-% to about 2 wt-% preservative and/or dye.

In a still further exemplary embodiment, a liquid rinse aid compositionaccording to the invention comprises from about 2 wt-% to about 60 wt-%surfactant system, from about 0 wt-% to about 15 wt-% coupling agent,from about 0 wt-% to about 8 wt-% water conditioning agent, from about 0wt-% to about 8 wt-% chelant, from about 0 wt-% to about 10 wt-%acidulant, from about 0 wt-% to about 80 wt-% water, and from about 0wt-% to about 2 wt-% preservative and/or dye.

In a still further exemplary embodiment, a liquid rinse aid compositionaccording to the invention comprises from about 2 wt-% to about 20 wt-%surfactant system, from about 0 wt-% to about 15 wt-% coupling agent,from about 0 wt-% to about 6 wt-% water conditioning agent, from about 0wt-% to about 6 wt-% chelant, from about 0 wt-% to about 10 wt-%acidulant, from about 0 wt-% to about 80 wt-% water, and from about 0wt-% to about 2 wt-% preservative and/or dye.

Carriers

In some embodiments, the compositions of the present invention areformulated as liquid compositions. Carriers can be included in suchliquid formulations. Any carrier suitable for use in a wetting agentcomposition can be used in the present invention. For example, in someembodiments the compositions include water as a carrier.

In some embodiments, liquid compositions according to the presentinvention will contain no more than about 98 wt % water, no more than 95wt % water, and typically no more than about 90 wt %. In otherembodiments, liquid compositions will contain at least 50 wt % water, orat least 60 wt % water as a carrier.

In further embodiments, the compositions may include a coupling agent inan amount in the range of up to about 80 wt-%, up to about 60 wt-%, upto about 40 wt-%, up to about 20 wt-%, up to about 15 wt-%, or up toabout 10 wt-%.

Hydrotropes

In some embodiments, the compositions of the present invention caninclude a hydrotrope. The hydrotrope may be used to aid in maintainingthe solubility of sheeting or wetting agents. Hydrotropes can also beused to modify the aqueous solution creating increased solubility forthe organic material. In some embodiments, hydrotropes are low molecularweight aromatic sulfonate materials such as xylene sulfonates,dialkyldiphenyl oxide sulfonate materials, and cumene sulfonates.

A hydrotrope or combination of hydrotropes can be present in thecompositions at an amount of from between about 1 wt % to about 50 wt %.In other embodiments, a hydrotrope or combination of hydrotropes can bepresent at about 10 wt % to about 30 wt % of the composition.

Hardening/Solidification Agents/Solubility Modifiers

In some embodiments, the compositions of the present invention caninclude a wetting agent and/or hardening agent (or a solidificationagent), as for example, an amide such stearic monoethanolamide or lauricdiethanolamide, or an alkylamide, and the like; a solid polyethyleneglycol, urea, or a solid EO/PO block copolymer, and the like; starchesthat have been made water-soluble through an acid or alkaline treatmentprocess; various inorganics that impart solidifying properties to aheated composition upon cooling, and the like. Such compounds may alsovary the solubility of the composition in an aqueous medium during usesuch that the wetting agent and/or other active ingredients may bedispensed from the solid composition over an extended period of time.

In some embodiments, a solidification agent includes a short chain alkylbenzene and/or alkyl naphthalene sulfonate, preferably sodium xylenesulfonate (SXS). In some embodiments SXS is employed as a dual purposematerial in that it acts as a coupler in solution but also as asolidifying agent as a powder.

A hardening agent or solidification agent can include one or more ofsodium xylene sulfonate, sodium toluene sulfonate, sodium cumenesulfonate, potassium toluene sulfonate, ammonium xylene sulfonate,calcium xylene sulfonate, sodium alkyl naphthalene sulfonate, and sodiumbutylnaphthalene sulfonate. In an aspect of the invention, the class ofshort chain alkyl benzene or alkyl naphthalene hydrotopes includes alkylbenzene sulfonates based on toluene, xylene, and cumene, and alkylnaphthalene sulfonates. Sodium toluene sulfonate and sodium xylenesulfonate are the best known hydrotopes. In a preferred embodiment thesolidification agent is SXS.

The compositions may include a solidification aid in an amount in therange of up to about 80 wt-%, from about 10 wt-% to about 80 wt-%, or upto about 50 wt-%. The compositions may include a solubility modifier inthe range of about 20 wt-% to about 40 wt-%, or about 5 to about 15wt-%.

Water Conditioning Agents

In some embodiments, the compositions of the present invention caninclude a water conditioning agent. Carboxylates such as citrate,tartrate or gluconate are suitable. Water conditioning polymers can beused as non-phosphorus containing builders. Exemplary water conditioningpolymers include, but are not limited to: polycarboxylates. Exemplarypolycarboxylates that can be used as builders and/or water conditioningpolymers include, but are not limited to: those having pendantcarboxylate (—CO₂—) groups such as polyacrylic acid, maleic acid,maleic/olefin copolymer, sulfonated copolymer or terpolymer,acrylic/maleic copolymer, polymethacrylic acid, acrylic acid-methacrylicacid copolymers, hydrolyzed polyacrylamide, hydrolyzedpolymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers,hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, andhydrolyzed acrylonitrile-methacrylonitrile copolymers. For a furtherdiscussion of water conditioning agents, see Kirk-Othmer, Encyclopediaof Chemical Technology, Third Edition, volume 5, pages 339-366 andvolume 23, pages 319-320, the disclosure of which is incorporated byreference herein. The compositions may include a water conditioningagent in an amount in the range of up to about 15 wt-%, up to about 10wt-%, or up to about 5 wt-%.

Acidulants

In some embodiments, the compositions of the present invention caninclude an acidulant or other pH buffer, and the like. The compositionscan be formulated such that during use in aqueous operations, forexample in aqueous cleaning operations, the rinse water will have adesired pH. For example, compositions designed for use in rinsing may beformulated such that during use in aqueous rinsing operation the rinsewater will have a pH in the range of 8.5 or below, 8.3 or below, or 7 orbelow. In other aspects, the pH is about 3 to about 5, or in the rangeof about 5 to about 8.5. Liquid product formulations in some embodimentshave a pH in the range of about 2 to about 4, or in the range of about 4to about 9. Techniques for controlling pH at recommended usage levelsinclude the use of buffers, alkali, acids, etc., and are well known tothose skilled in the art. One example of a suitable acid for controllingpH includes citric acid, hydrochloric acid, phosphoric acid, sodiumbicarbonate, protonated forms of phosphonates, sodium benzoate andgluconic acid. The compositions may include an acidulant water in anamount in the range of up to about 20 wt-%, up to about 15 wt-%, up toabout 10 wt-%, or up to about 5 wt-%.

Chelating/Sequestering Agents

In some embodiments, the compositions of the present invention caninclude one or more chelating/sequestering agents, which may also bereferred to as a builder. A chelating/sequestering agent may include,for example an aminocarboxylic acid, aminocarboxylates and theirderivatives, a condensed phosphate, a phosphonate, a polyacrylate, andmixtures and derivatives thereof. In general, a chelating agent is amolecule capable of coordinating (i.e., binding) the metal ions commonlyfound in natural water to prevent the metal ions from interfering withthe action of the other ingredients of a wetting agent or other cleaningcomposition. The chelating/sequestering agent may also function as athreshold agent when included in an effective amount.

The composition may include a phosphonate such as1-hydroxyethane-1,1-diphosphonic acid CH₃C(OH)[PO(OH)₂]₂;aminotri(methylenephosphonic acid) N[CH₂PO(OH)₂]₃;aminotri(methylenephosphonate), sodium salt;2-hydroxyethyliminobis(methylenephosphonic acid) HOCH₂CH₂N[CH₂PO(OH)₂]₂;diethylenetriaminepenta(methylenephosphonic acid)(HO)₂POCH₂N[CH₂N[CH₂PO(OH)₂]₂]₂;diethylenetriaminepenta(methylenephosphonate), sodium salt C₉H_((28-x))N₃Na_(x)O₁₅P₅ (x=7); hexamethylenediamine(tetramethylenephosphonate),potassium salt C₁₀H_((28-x))N₂K_(x)O₁₂P₄ (x=6);bis(hexamethylene)triamine(pentamethylenephosphonic acid)(HO₂)POCH₂N[(CH₂)₆N[CH₂PO(OH)₂]₂]₂; and phosphorus acid H₃PO₃. In someembodiments, a phosphonate combination such as ATMP and DTPMP may beused. A neutralized or alkaline phosphonate, or a combination of thephosphonate with an alkali source prior to being added into the mixturesuch that there is little or no heat or gas generated by aneutralization reaction when the phosphonate is added can be used. Someexamples of polymeric polycarboxylates suitable for use as sequesteringagents include those having a pendant carboxylate (—O₂) groups andinclude, for example, polyacrylic acid, maleic/olefin copolymer,acrylic/maleic copolymer, polymethacrylic acid, acrylic acid-methacrylicacid copolymers, hydrolyzed polyacrylamide, hydrolyzedpolymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers,hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile,hydrolyzed acrylonitrile-methacrylonitrile copolymers, and the like.

The composition may include an aminocarboxylate or its derivatives,including for example sodium aminocarboxylate under the tradename TrilonA® available from BASF. A biodegradable aminocarboxylate or derivativethereof may also be included in the composition, including for examplethose available under the tradename Trilon available from BASF.

In some embodiments, the compositions can include in the range of up toabout 70 wt-%, or in the range of about 0.1 to about 60 wt-%, or about0.1 to about 5.0 wt-%, of a chelating/sequestering agent. In someembodiments, the compositions of the invention include less than about1.0 wt-%, or less than about 0.5 wt-% of a chelating/sequestering agent.In other embodiments the compositions may include a chelant/sequesteringagent in an amount in the range of up to about 10 wt-%, or up to about 5wt-%.

Anti-Microbial/Sanitizing Agents

In some embodiments, the compositions of the present invention caninclude an antimicrobial agent. The antimicrobial agent can be providedin a variety of ways. For example, in some embodiments, theantimicrobial agent is included as part of the wetting agentcomposition. In other embodiments, the antimicrobial agent can beincluded as a separate component of a composition including the wettingagent composition.

Antimicrobial agents are chemical compositions that can be used in afunctional material to prevent microbial contamination and deteriorationof material systems, surfaces, etc. Generally, these materials fall inspecific classes including phenolics, halogen compounds, quaternaryammonium compounds, metal derivatives, amines, alkanol amines, nitroderivatives, analides, organosulfur and sulfur-nitrogen compounds andmiscellaneous compounds.

In some embodiments, antimicrobial agents suitable for use with thesurfactant systems of the present invention include percarboxylic acidcompositions or peroxygen compounds, and/or mixtures of diesters. Forexample, in some embodiments the antimicrobial agent included is atleast one of peracetic acid, peroctanoic acid, and mixtures andderivatives thereof. In other embodiments, the sanitizing and/orantimicrobial agent may be a two solvent antimicrobial composition suchas the composition disclosed in U.S. Pat. No. 6,927,237, the entirecontents of which are hereby incorporated by reference.

In other embodiments, the sanitizing and/or antimicrobial agent mayinclude compositions of mono- or diester dicarboxylates. Suitable mono-or diester dicarboxylates include mono- or dimethyl, mono- or diethyl,mono- or dipropyl (n- or iso), or mono- or dibutyl esters (n-, sec, ortert), or amyl esters (n-, sec-, iso-, or tert-) of malonic, succinic,glutaric, adipic, or sebacic acids, or mixtures thereof. Mixed esters(e.g., monomethyl/monoethyl, or monopropyl/monoethyl) can also beemployed. Preferred mono- or diester dicarboxylates are commerciallyavailable and soluble in water or another carrier at concentrationseffective for antimicrobial activity. Preferred mono- or diesterdicarboxylates are toxic to microbes but do not exhibit unacceptabletoxicity to humans under formulation or use conditions. Exemplarycompositions including mono- or diester dicarboxylates are disclosed inU.S. Pat. No. 7,060,301, the entire contents of which are herebyincorporated by reference.

Some examples of common sanitizing and/or antimicrobial agents includephenolic antimicrobials such as pentachlorophenol, orthophenylphenol, achloro-p-benzylphenol, p-chloro-m-xylenol. Halogen containingantibacterial agents include sodium trichloroisocyanurate, sodiumdichloro isocyanate (anhydrous or dihydrate),iodine-poly(vinylpyrolidinone) complexes, bromine compounds such as2-bromo-2-nitropropane-1,3-diol, and quaternary antimicrobial agentssuch as benzalkonium chloride, didecyldimethyl ammonium chloride,choline diiodochloride, tetramethyl phosphonium tribromide. Otherantimicrobial compositions such ashexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates suchas sodium dimethyldithiocarbamate, and a variety of other materials areknown in the art for their antimicrobial properties. In someembodiments, the rinse aid compositions are dosed in combination with asanitizing agent (such as for low temperature applications of use) orfurther comprise sanitizing agent in an amount effective to provide adesired level of sanitizing.

Additional examples of common sanitizing and/or antimicrobial agentsinclude chlorine-containing compounds such as a chlorine, ahypochlorite, chloramines, of the like.

In some embodiments, an antimicrobial component, can be included in therange of up to about 75% by wt. of the composition, up to about 20 wt.%, in the range of about 1.0 wt % to about 20 wt %, in the range ofabout 5 wt % to about 10 wt %, in the range of about 0.01 to about 1.0wt. %, or in the range of 0.05 to 0.05 wt % of the composition.

Bleaching Agents

In some embodiments, the compositions of the present invention caninclude a bleaching agent. Bleaching agents can be used for lighteningor whitening a substrate, and can include bleaching compounds capable ofliberating an active halogen species, such as Cl₂, Br₂, —OCl⁻ and/or—OBr⁻, or the like, under conditions typically encountered during thecleansing process. Suitable bleaching agents for use can include, forexample, chlorine-containing compounds such as a chlorine, ahypochlorite, chloramines, of the like. Some examples ofhalogen-releasing compounds include the alkali metaldichloroisocyanurates, chlorinated trisodium phosphate, the alkali metalhypochlorites, monochloramine and dichloroamine, and the like.Encapsulated chlorine sources may also be used to enhance the stabilityof the chlorine source in the composition.

A bleaching agent may also include an agent containing or acting as asource of active oxygen. The active oxygen compound acts to provide asource of active oxygen, for example, may release active oxygen inaqueous solutions. An active oxygen compound can be inorganic ororganic, or can be a mixture thereof. Some examples of active oxygencompound include peroxygen compounds, or peroxygen compound adducts.Some examples of active oxygen compounds or sources include hydrogenperoxide, perborates, sodium carbonate peroxyhydrate, phosphateperoxyhydrates, potassium permonosulfate, and sodium perborate mono andtetrahydrate, with and without activators such as tetraacetylethylenediamine, and the like. A wetting agent composition may include a minorbut effective amount of a bleaching agent, for example, in someembodiments, in the range of up to about 10 wt-%, and in someembodiments, in the range of about 0.1 to about 6 wt-%.

Builders or Fillers

In some embodiments, the compositions of the present invention caninclude a minor but effective amount of one or more of a filler whichdoes not necessarily perform as a rinse and/or cleaning agent per se,but may cooperate with the surfactant systems to enhance the overallcapacity of the composition. Some examples of suitable fillers mayinclude sodium sulfate, sodium chloride, starch, sugars, C₁-C₁₀ alkyleneglycols such as propylene glycol, and the like. In some embodiments, afiller can be included in an amount in the range of up to about 20 wt-%,and in some embodiments, in the range of about 1-15 wt-%.

Anti-Redeposition Agents

In some embodiments, the compositions of the present invention caninclude an anti-redeposition agent capable of facilitating sustainedsuspension of soils in a rinse solution and preventing removed soilsfrom being redeposited onto the substrate being rinsed. Some examples ofsuitable anti-redeposition agents can include fatty acid amides,fluorocarbon surfactants, complex phosphate esters, styrene maleicanhydride copolymers, and cellulosic derivatives such as hydroxyethylcellulose, hydroxypropyl cellulose, and the like. A wetting agentcomposition may include up to about 10 wt-%, and in some embodiments, inthe range of about 1 to about 5 wt-%, of an anti-redeposition agent.

Dyes/Odorants

In some embodiments, the compositions of the present invention caninclude dyes, odorants including perfumes, and other aesthetic enhancingagents. Dyes may be included to alter the appearance of the composition,as for example, FD&C Blue 1 (Sigma Chemical), FD&C Yellow 5 (SigmaChemical), Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.),Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keyston Analineand Chemical), Metanil Yellow (Keystone Analine and Chemical), Acid Blue9 (Hilton Davis), Sandolan Blue/Acid Blue 182 (Sandoz), Hisol Fast Red(Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical),Acid Green 25 (Ciba-Geigy), and the like. Fragrances or perfumes thatmay be included in the compositions include, for example, terpenoidssuch as citronellol, aldehydes such as amyl cinnamaldehyde, a jasminesuch as C1S-jasmine or jasmal, vanillin, and the like. In otherembodiments the compositions may include a preservative and/or dye in anamount in the range of up to about 2 wt-%, or up to about 1 wt-%.

Humectant

The composition can also optionally include one or more humectant. Ahumectant is a substance having an affinity for water. The humectant canbe provided in an amount sufficient to aid in reducing the visibility ofa film on the substrate surface. The visibility of a film on substratesurface is a particular concern when the rinse water contains in excessof 200 ppm total dissolved solids. Accordingly, in some embodiments, thehumectant is provided in an amount sufficient to reduce the visibilityof a film on a substrate surface when the rinse water contains in excessof 200 ppm total dissolved solids compared to a rinse agent compositionnot containing the humectant. The terms “water solids filming” or“filming” refer to the presence of a visible, continuous layer of matteron a substrate surface that gives the appearance that the substratesurface is not clean.

Some example humectants that can be used include those materials thatcontain greater than 5 wt. % water (based on dry humectant) equilibratedat 50% relative humidity and room temperature. Exemplary humectants thatcan be used include glycerin, propylene glycol, sorbitol, alkylpolyglycosides, polybetaine polysiloxanes, and mixtures thereof. In someembodiments, the wetting agent composition can include humectant in anamount in the range of up to about 75% based on the total composition,and in some embodiments, in the range of about 5 wt. % to about 75 wt. %based on the weight of the composition. In some embodiments, wherehumectant is present, the weight ratio of the humectant to the sheetingagent can be in the range of about 1:3 or greater, and in someembodiments, in the range of about 5:1 and about 1:3.

EMBODIMENTS

The surfactant system compositions of the present invention may includeliquid products, thickened liquid products, gelled liquid products,paste, granular and pelletized solid compositions, powders, pressedsolid compositions, solid block compositions, cast solid blockcompositions, extruded solid block composition and others.

Use Solutions

The surfactant system compositions may include concentrate compositionsor may be diluted to form use compositions. In general, a concentraterefers to a composition that is intended to be diluted with water toprovide a use solution that contacts an object to provide the desiredcleaning, rinsing, or the like. The composition that contacts thearticles to be washed can be referred to as a concentrate or a usecomposition (or use solution) dependent upon the formulation employed inmethods according to the invention. In an aspect, the surfactant systemsin a use solution preferably have a pH of 8.5 or below, 8.3 or below, or7 or below.

A use solution may be prepared from the concentrate by diluting theconcentrate with water at a dilution ratio that provides a use solutionhaving desired detersive properties. The water that is used to dilutethe concentrate to form the use composition can be referred to as waterof dilution or a diluent, and can vary from one location to another. Thetypical dilution factor is between approximately 1 and approximately10,000 but will depend on factors including water hardness, the amountof soil to be removed and the like. In an embodiment, the concentrate isdiluted at a ratio of between about 1:10 and about 1:10,000 concentrateto water. Particularly, the concentrate is diluted at a ratio of betweenabout 1:100 and about 1:5,000 concentrate to water. More particularly,the concentrate is diluted at a ratio of between about 1:250 and about1:2,000 concentrate to water.

In an aspect of the invention, the surfactant system compositionpreferably provides efficacious rinsing at low use dilutions, i.e.,require less volume to clean effectively. In an aspect, a concentratedliquid detergent composition may be diluted in water prior to use atdilutions ranging from about 1/16 oz./gal. to about 2 oz./gal. or more.Beneficially the surfactant system concentrate composition according tothe invention is efficacious at low actives, such that the compositionprovides at least substantially similar effects, and preferably improvedeffects, in comparison to conventional rinsing surfactant systems. In anaspect of the invention, a use solution of the surfactant systemcomposition has between about 1 ppm to about 125 ppm surfactant system,between about 1 ppm to about 100 ppm surfactant system, between about 1ppm to about 75 ppm surfactant system, between about 1 ppm to about 50ppm surfactant system, and preferably between about 10 ppm to about 50ppm surfactant system. In addition, without being limited according tothe invention, all ranges recited are inclusive of the numbers definingthe range and include each integer within the defined range.

Solid Compositions and Methods of Making the Solids

Various solid compositions can be formulated using the surfactantsystems of the present invention, including granular and pelletizedsolid compositions, powders, solid block compositions, cast solid blockcompositions, extruded solid block composition and others. By the term“solid”, it is meant that the hardened composition will not flow andwill substantially retain its shape under moderate stress or pressure ormere gravity. A solid may be in various forms such as a powder, a flake,a granule, a pellet, a tablet, a lozenge, a puck, a briquette, a brick,a solid block, a unit dose, or another solid form known to those ofskill in the art. The degree of hardness of the solid cast compositionand/or a pressed solid composition may range from that of a fused solidproduct which is relatively dense and hard, for example, like concrete,to a consistency characterized as being a hardened paste. In addition,the term “solid” refers to the state of the detergent composition underthe expected conditions of storage and use of the solid detergentcomposition. In general, it is expected that the detergent compositionwill remain in solid form when exposed to temperatures of up toapproximately 100° F. and particularly up to approximately 120° F.

The resulting solid composition may take forms including, but notlimited to: a cast solid product; an extruded, molded or formed solidpellet, block, tablet, powder, granule, flake; pressed solid; or theformed solid can thereafter be ground or formed into a powder, granule,or flake. In an exemplary embodiment, extruded pellet materials formedby the solidification matrix have a weight of between approximately 50grams and approximately 250 grams, extruded solids formed by thecomposition have a weight of approximately 100 grams or greater, andsolid block detergents formed by the composition have a mass of betweenapproximately 1 and approximately 10 kilograms. The solid compositionsprovide for a stabilized source of functional materials. In someembodiments, the solid composition may be dissolved, for example, in anaqueous or other medium, to create a concentrated and/or use solution.The solution may be directed to a storage reservoir for later use and/ordilution, or may be applied directly to a point of use.

Solid particulate materials can be made by merely blending the dry solidingredients in appropriate ratios or agglomerating the materials inappropriate agglomeration systems. Pelletized materials can bemanufactured by compressing the solid granular or agglomerated materialsin appropriate pelletizing equipment to result in appropriately sizedpelletized materials. Solid block and cast solid block materials can bemade by introducing into a container either a prehardened block ofmaterial or a castable liquid that hardens into a solid block within acontainer. Preferred containers include disposable plastic containers orwater soluble film containers. Other suitable packaging for thecomposition includes flexible bags, packets, shrink wrap, and watersoluble film such as polyvinyl alcohol.

The solid detergent compositions may be formed using a batch orcontinuous mixing system. In an exemplary embodiment, a single- ortwin-screw extruder is used to combine and mix one or more components athigh shear to form a homogeneous mixture. In some embodiments, theprocessing temperature is at or below the melting temperature of thecomponents. The processed mixture may be dispensed from the mixer byforming, casting or other suitable means, whereupon the detergentcomposition hardens to a solid form. The structure of the matrix may becharacterized according to its hardness, melting point, materialdistribution, crystal structure, and other like properties according toknown methods in the art. Generally, a solid detergent compositionprocessed according to the method of the invention is substantiallyhomogeneous with regard to the distribution of ingredients throughoutits mass and is dimensionally stable.

In an extrusion process, the liquid and solid components are introducedinto final mixing system and are continuously mixed until the componentsform a substantially homogeneous semi-solid mixture in which thecomponents are distributed throughout its mass. The mixture is thendischarged from the mixing system into, or through, a die or othershaping means. The product is then packaged. In an exemplary embodiment,the formed composition begins to harden to a solid form in betweenapproximately 1 minute and approximately 3 hours. Particularly, theformed composition begins to harden to a solid form in betweenapproximately 1 minute and approximately 2 hours. More particularly, theformed composition begins to harden to a solid form in betweenapproximately 1 minute and approximately 20 minutes.

In a casting process, the liquid and solid components are introducedinto the final mixing system and are continuously mixed until thecomponents form a substantially homogeneous liquid mixture in which thecomponents are distributed throughout its mass. In an exemplaryembodiment, the components are mixed in the mixing system for at leastapproximately 60 seconds. Once the mixing is complete, the product istransferred to a packaging container where solidification takes place.In an exemplary embodiment, the cast composition begins to harden to asolid form in between approximately 1 minute and approximately 3 hours.Particularly, the cast composition begins to harden to a solid form inbetween approximately 1 minute and approximately 2 hours. Moreparticularly, the cast composition begins to harden to a solid form inbetween approximately 1 minute and approximately 20 minutes.

In a pressed solid process, a flowable solid, such as granular solids orother particle solids including the surfactant systems and bindingagents (e.g. hydrated chelating agent, such as a hydratedaminocarboxylate, a hydrated polycarboxylate or hydrated anionicpolymer, a hydrated citrate salt or a hydrated tartrate salt, or thelike together with an alkali metal carbonate, such as disclosed in U.S.Pat. Nos. 8,894,897 and 8,894,898, which are herein incorporated byreference in its entirety) are combined under pressure. The surfactantsystems are particularly well suited for use in pressed solidcompositions due to the lower liquid amounts to be included as a resultof the synergy afforded by the formulation of the surfactant systemsrequiring lower actives (i.e. less surfactant that other rinse aidsurfactant compositions). According to a non-limiting example, a pressedsolid according to the surfactant systems of the present inventionincludes substantially less liquid (e.g. less than 30%, 10-30%, lessthan 20%, 10-20%, 5-20%, less than 10%, 5-10%, or less than 5%) incomparison to a conventional block solid surfactant system would requirebetween about 50-70% liquid.

In a pressed solid process, flowable solids of the compositions areplaced into a form (e.g., a mold or container). The method can includegently pressing the flowable solid in the form to produce the solidcleaning composition. Pressure may be applied by a block machine or aturntable press, or the like. Pressure may be applied at about 1 toabout 2000 psi, about 1 to about 300 psi, about 5 psi to about 200 psi,or about 10 psi to about 100 psi. In certain embodiments, the methodscan employ pressures as low as greater than or equal to about 1 psi,greater than or equal to about 2, greater than or equal to about 5 psi,or greater than or equal to about 10 psi. As used herein, the term “psi”or “pounds per square inch” refers to the actual pressure applied to theflowable solid being pressed and does not refer to the gauge orhydraulic pressure measured at a point in the apparatus doing thepressing. The method can include a curing step to produce the solidcleaning composition. As referred to herein, an uncured compositionincluding the flowable solid is compressed to provide sufficient surfacecontact between particles making up the flowable solid that the uncuredcomposition will solidify into a stable solid cleaning composition. Asufficient quantity of particles (e.g., granules) in contact with oneanother provides binding of particles to one another effective formaking a stable solid composition. Inclusion of a curing step mayinclude allowing the pressed solid to solidify for a period of time,such as a few hours, or about 1 day (or longer). In additional aspects,the methods could include vibrating the flowable solid in the form ormold, such as the methods disclosed in U.S. Pat. No. 8,889,048, which isherein incorporated by reference in its entirety.

The use of pressed solids provide numerous benefits over conventionalsolid block or tablet compositions requiring high pressure in a tabletpress, or casting requiring the melting of a composition consumingsignificant amounts of energy, and/or by extrusion requiring expensiveequipment and advanced technical know-how. Pressed solids overcome suchvarious limitations of other solid formulations for which there is aneed for making solid cleaning compositions. Moreover, pressed solidcompositions retain its shape under conditions in which the compositionmay be stored or handled.

The following patents disclose various combinations of solidification,binding and/or hardening agents that can be utilized in the solidcleaning compositions of the present invention. The following U.S.patents are incorporated herein by reference: U.S. Pat. Nos. 7,153,820;7,094,746; 7,087,569; 7,037,886; 6,831,054; 6,730,653; 6,660,707;6,653,266; 6,583,094; 6,410,495; 6,258,765; 6,177,392; 6,156,715;5,858,299; 5,316,688; 5,234,615; 5,198,198; 5,078,301; 4,595,520;4,680,134; RE32,763; and RE32818.

Methods of Use

The surfactant systems and compositions employing the same can be usedfor a variety of domestic/consumer applications as well as industrialapplications. The compositions can be applied in a variety of areasincluding kitchens, bathrooms, factories, hospitals, dental offices,pharmaceutical plants or co-packers, and food plants or co-packers, andcan be applied to a variety of hard or soft surfaces having smooth,irregular or porous topography. Suitable hard surfaces include, forexample, architectural surfaces (e.g., floors, walls, windows, sinks,tables, counters and signs); eating utensils; hard-surface medical orsurgical instruments and devices; and hard-surface packaging. Such hardsurfaces can be made from a variety of materials including, for example,ceramic, metal, glass, wood or hard plastic. Suitable soft surfacesinclude, for example paper, filter media, hospital and surgical linensand garments, soft-surface medical or surgical instruments and devices,and soft-surface packaging. Such soft surfaces can be made from avariety of materials including, for example, paper, fiber, woven ornonwoven fabric, soft plastics and elastomers.

The surfactant systems and compositions employing the same of theinvention can be used in a variety of applications. For example, in someembodiments, the surfactant systems and compositions can be formulatedfor use in warewashing applications, including rinse cycles incommercial warewashing machines. A first type of rinse cycle can bereferred to as a hot water sanitizing rinse cycle because of the use ofgenerally hot rinse water (about 180° F.). A second type of rinse cyclecan be referred to as a chemical sanitizing rinse cycle and it usesgenerally lower temperature rinse water (about 120° F.). Beneficially,the surfactant systems and compositions employing the same areparticularly well suited for use in both low and high temperatureconditions.

The methods of employing the surfactant systems and compositionsemploying the surfactant systems are particularly suited for use inclosed systems, e.g. dish or ware washing systems for obtaining enhancedsheeting, wetting and drying on articles and surfaces. According toembodiments of the invention the surfactant systems and compositionsemploying the surfactant systems are suitable for both low temperatureand high temperature applications.

In an aspect according to the invention, the surfactant systems andcompositions employing the surfactant systems as disclosed herein areemployed in low temperature warewash applications. As referred toherein, low temperature warewash includes was temperatures at or belowabout 140° F. In an embodiment, the temperature of the rinse water is upto about 140° F., preferably in the range of 100° F. to 140° F.,preferably in the range of 110° F. to 140° F., and most preferably inthe range of 120° F. to 140° F. As referred to herein, “low temperature”refers to those rinse water temperatures below about 140° F. In anaspect, the methods of the invention employing a low temperature furtheremploy a sanitizer.

In a particularly preferred aspect, low temperature compositions mayemploy a combination of Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (orSurfactant A2 (R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H)and Surfactant D (R⁷—O—(PO)y₅(EO)x₅(PO)y₆). In a further embodimentSurfactant E (R⁶—O—(PO)y₄(EO)x₄) is excluded from the low temperaturerinse aid surfactant system. In a further embodiment, for a solidcomposition Surfactant G ((EO)_(x6) (PO)_(y7)(EO)_(x6)), an EO-PO-EOblock copolymer, is included.

In an aspect according to the invention, the surfactant systems andcompositions employing the surfactant systems as disclosed herein areemployed in high temperature warewash applications. As referred toherein, high temperature (or sanitizing) rinse includes temperaturesabove about 140° F. In an aspect, high temperature refers to a rinsetemperature for ware washing above 140° F., or from about 140° F. toabout 190° F., or from about 145° F. to about 180° F.

In a particularly preferred aspect, high temperature compositions mayemploy a combination of Surfactant A (R¹—O-(EO)_(x3)(PO)_(y3)—H) (orSurfactant A2 (R¹—O-(EO)x₄(PO)y₄-H)), Surfactant B (R²—O-(EO)_(x1)—H)and Surfactant C(R²—O-(EO)_(x2)—H). In a further embodiment Surfactant E(R⁶—O—(PO)y₄(EO)x₄) is excluded from the high temperature rinse aidsurfactant system. In a further embodiment, for a solid compositionSurfactant G ((EO)_(x6) (PO)_(y7)(EO)_(x6)), an EO-PO-EO blockcopolymer, is included.

The surfactant systems and compositions employing the surfactant systemscan contact the surface or article by numerous methods for applying acomposition, such as spraying the composition, immersing the object inthe composition, or a combination thereof. A concentrate or useconcentration of a composition of the present invention can be appliedto or brought into contact with an article by any conventional method orapparatus for applying a cleaning composition to an object. For example,the object can be wiped with, sprayed with, and/or immersed in thecomposition, or a use solution made from the composition. Thecomposition can be sprayed, or wiped onto a surface; the composition canbe caused to flow over the surface, or the surface can be dipped intothe composition. Contacting can be manual or by machine.

In other embodiments, the surfactant systems and compositions employingthe same can be used in a high solids containing water environment inorder to reduce the appearance of a visible film caused by the level ofdissolved solids provided in the water. In general, high solidscontaining water is considered to be water having a total dissolvedsolids (TDS) content in excess of 200 ppm. In certain localities, theservice water contains a total dissolved solids content in excess of 400ppm, and even in excess of 800 ppm. The applications where the presenceof a visible film after washing a substrate is a particular problemincludes the restaurant or warewashing industry, the car wash industry,and the general cleaning of hard surfaces.

Exemplary articles in the warewashing industry that can be treated witha surfactant systems and compositions employing the same includeplastics, dishware, cups, glasses, flatware, and cookware. For thepurposes of this invention, the terms “dish” and “ware” are used in thebroadest sense to refer to various types of articles used in thepreparation, serving, consumption, and disposal of food stuffs includingpots, pans, trays, pitchers, bowls, plates, saucers, cups, glasses,forks, knives, spoons, spatulas, and other glass, metal, ceramic,plastic composite articles commonly available in the institutional orhousehold kitchen or dining room. In general, these types of articlescan be referred to as food or beverage contacting articles because theyhave surfaces which are provided for contacting food and/or beverage.When used in these warewashing applications, the surfactant systemsprovide effective sheeting action, low foaming properties and fastdrying. In some aspects, the surfactant system and compositionsemploying the same dries a surface (e.g. ware) within about 30 secondsto a few minutes, or within about 30 to about 90 seconds after theaqueous solution is applied.

In addition to having the desirable properties described above, it mayalso be useful for the surfactant systems and compositions employing thesame to be biodegradable, environmentally friendly, and generallynontoxic. A wetting agent of this type may be described as being “foodgrade”.

The surfactant systems and compositions employing the same may also beapplied to surfaces and objects other than ware, including, but notlimited to, medical and dental instruments, and hard surfaces such asvehicle surfaces or any other facility surfaces, textiles and laundry,use in mining and/or other industrial energy services. The compositionsmay also be used as rinse aids in a variety of applications for avariety of surfaces, e.g., included in compositions used to sanitize,disinfect, act as a sporicide for, or sterilize bottles, pumps, lines,tanks and mixing equipment used in the manufacture of such beverages.Still further, the surfactant systems and compositions employing thesame are particularly suitable for use as rinse aids, including glasscleaners. These are other applications of use are included within thescope of the present invention.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated as incorporated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

Example 1

Glewwe foam evaluation. Potential raw materials for rinse aids wereinitially tested in a Glewwe foam machine. The raw materials were testedin the Glewwe foam machine by themselves initially and then in differentcombination ratios with other raw materials based on activity of thespecific raw material. The raw material(s) was added to the circulatingwater, and the foam generated was measured after one minute and fiveminutes. Products that produce excessive amounts of stable foam in thisevaluation were identified as undesirable as they cause machine pumpcavitation.

Table 4 shows initial testing of individual surfactants for foaming. Thefoam profiles indicate how much foam is generated by each individualsurfactant at different temperatures to give a better understanding ofhow it will foam in a dish machine. The foam studies were completedusing the Glewwe foam apparatus where foam level was read after oneminute of agitation and again after 5 minutes of agitation. The Glewwefoam apparatus was set at 6 psi for 5 minutes at varied temperatures (°C.). The machine was then shut off and foam was measured for 1 minute.Test were run in soft water (3 L), used 20 g powdered milk and 50 ppmactive surfactant (at 100% actives level). The initial 1 minute testingshows foaming with surfactant only; the soil challenge after 5 minutesincluded presence of 2000 ppm soil and measured foaming with surfactantin presence of soil (indicative of foam measurement wherein a desirablefoam profile is less than 5 inches.

TABLE 4 After 1 min run After 5 (total) min Rinse time (inches); runtime; Aid surfactant only soil challenge Surfac- Temp grams 15 1 15 1tant (° C.) used Initial sec min Initial sec min F 60 0.15 1 3/4  0 0 87 ¾ 7 ¼ G 60 0.15 10 10 9 — — — H 48 0.15  0  0 0 1 0 0 H 60 0.15  0  00 1 ¼ 0 0 H 71 0.15  0  0 0 3 1 0 D 48 0.15  0  0 0 Trace 0 0 D 71 0.15 0  0 0 3 0 0 A 48 0.15  1 ¼ 1/8 5 3 ¾ 2 ½ A 60 0.15  0  0 0 5 3 ½ 1 ½ A71 0.15  0  0 0 3 ½ 1 ¼ J 48 0.15 ¾ ¼ ¼ 3 1 ¼ ¾ J 60 0.15  0  0 0 3 ¾ ½J 71 0.15  0  0 0 3 ¾ ½ I 48 0.15  0  0 0 2 Trace 0 I 60 0.15 Trace  0 03 ½ >1/18 I 71 0.15 Trace  0 0 4 2 ½ ½

The foam level in the machine was noted. In reference to the resultsshown in Table 4, the amount of foam in inches indicates how much foamremains, wherein a minimal amount is preferred after 1 minute and 15minutes. Partially stable foam broke down slowly within a minute.Unstable foam broke rapidly, within less the 15 seconds. The bestresults were unstable foam or no foam, as generally, stable foam at anylevel is unacceptable. Foam that is less than one half of an inch andthat is unstable and breaks to nothing soon after the machine is shutoff is acceptable, but no foam is best. Various surfactants demonstratedbeneficial low- or no-foam profiles under the testing conditions. Thesurfactants were then advanced for sheeting evaluation.

Example 2

Sheeting evaluation. The individual surfactants evaluated in Example 1for foaming were also evaluated for sheeting in a dish machine to showindividual capacity to sheet different types of dish ware. The testobserves water sheeting on twelve different types of warewash materials,including: 10 oz. glass tumbler, a china dinner plate, a melamine dinnerplate, a polypropylene coffee cup, a dinex bowl, a polypropylene jug, apolysulfonate dish, a stainless steel butter knife, a polypropylene cafétray, a fiberglass café tray and a stainless steel slide 316.

For the evaluation the test materials are initially cleaned and thensoiled with a solution containing a 0.2% hotpoint soil (mixture ofpowder milk and margarine). The materials were then exposed to 30 secondwash cycles using 71° C. (160° F.) soft water (0 grain) (for hightemperature evaluations) or 48° C. (120° F.) and 60° C. (140° F.) citywater (for low temperature evaluations). The test product is measured inparts per million actives. Immediately after the warewash materials areexposed to the test product the appearance of the water draining off ofthe individual test materials (sheeting) is examined.

The results for evaluation of the individual surfactants are shown inTables 5-8. Immediately after the ware wash materials were exposed tothe rinse aid formulations, the appearance of the water draining off ofthe individual ware wash materials (sheeting) was examined andevaluated. The tables below show the results of these tests. In thesetables, the sheeting evaluation is indicated by either a zero (0)signifying no sheeting, the number “one” (1) signifying pin holesheeting, or the number “two” (2) signifying complete sheeting. Pinholesheeting refers to the appearance of tiny pinholes on the surface of thewater, as the water is draining off of the washed article. These holesincrease slightly in size as the water continues to drain off the ware.Complete sheeting refers to a continuous sheet of water on the washedarticle as the water drains off the ware. The test was complete when allof the washed articles display complete sheeting.

TABLE 5 (Surfactant D, 0 grain, 69.4° C. (157° F.)) ppm, Actives inRinse Aid 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200Glass tumbler 0 0 0 0 0 0 1 1 1 1 1 1 1 1 1 1 1 China Plate 0 0 0 1 1 11 1 1 1 1 1 1 1 1 1 1 Melamine 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 PlatePolypropylene 0 0 0 0 1 1 1 1 1 1 1 1 1 1 1 1 1 Cup (yellow) Dinex Bowl0 — 1 1 1 1 1 1 1 1 1 1 1 2 2 2 2 (blue) Polypropylene 0 1 1 1 1 1 1 1 11 1 2 2 2 2 2 2 Jug (blue) Polysulfonate 0 0 0 0 1 1 1 1 1 1 1 1 1 1 1 11 Dish (clear tan) Stainless 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 SteelKnife Polypropylene 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 tray (peach)Fiberglass tray 0 0 0 0 0 0 1 1 1 1 2 2 2 2 2 2 2 (tan) Stainless steel0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 slide 316 Suds No No No No No No No NoNo No No No No No No No No

TABLE 6 Surfactant A; 0 grain; 69.4° C. (157° F.)) shows completesheeting achieved at 110 ppm for all substrates. ppm, Actives in RinseAid 40 50 60 70 80 90 100 110 Glass tumbler 0 0 0 1 1 2 2 2 China Plate1 1 1 1 2 2 2 2 Melamine Plate 1 1 1 1 2 2 2 2 Polypropylene Cup 0 0 0 00 1 1 2 (yellow) Dinex Bowl (blue) 0 0 0 0 0 1 1 2 Polypropylene Jug 0 01 1 1 2 2 2 (blue) Polysulfonate Dish 0 0 1 1 1 2 2 2 (clear tan)Stainless Steel Knife 0 1 1 1 1 2 2 2 Polypropylene tray 1 1 1 1 1 2 2 2(peach) Fiberglass tray (tan) 0 0 1 1 1 2 2 2 Stainless steel slide 1 11 1 1 2 2 2 316 Suds No No No No No No No No

TABLE 7 (Surfactant I; 0 grain; 69.4° C. (157° F.); T = trace) ppm,Actives in Rinse Aid 40 50 60 70 80 90 100 110 120 130 Glass tumbler 0 00 1 1 1 1 2 2 2 China Plate 0 1 1 1 1 2 2 2 2 2 Melamine Plate 0 1 1 1 11 2 2 2 2 Polypropylene Cup 0 0 0 0 0 0 1 1 1 2 (yellow) Dinex Bowl(blue) 0 0 0 1 1 2 2 2 2 2 Polypropylene Jug 0 0 0 1 1 1 1 1 1 2 (blue)Polysulfonate Dish 0 0 0 1 1 1 1 2 2 2 (clear tan) Stainless Steel Knife0 1 1 1 1 1 1 1 1 2 Polypropylene tray 0 1 1 1 1 2 2 2 2 2 (peach)Fiberglass tray (tan) 0 0 0 1 1 1 1 1 1 1 Stainless steel slide 0 1 1 11 1 1 1 2 2 316 Suds T T T T T T T T T T

TABLE 8 (Surfactant J; 0 grain 69.4° C. (157° F.)) ppm, Actives in RinseAid 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 Glass0 0 0 0 1 1 1 1 1 1 1 1 1 2 2 2 2 tumbler China Plate 0 0 0 1 1 1 1 1 11 1 1 1 1 1 1 1 Melamine 0 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 PlatePolypropylene 0 0 0 0 0 1 1 1 1 1 1 1 1 1 1 1 1 Cup (yellow) Dinex Bowl0 0 0 0 1 1 1 1 1 1 1 1 1 1 1 1 1 (blue) Polypropylene 0 0 0 1 1 1 1 1 11 1 1 1 1 1 1 1 Jug (blue) Polysulfonate 0 0 0 0 1 1 1 1 1 1 1 1 1 1 1 11 Dish (clear tan) Stainless 0 0 0 1 1 1 1 1 1 1 1 1 1 1 2 2 2 SteelKnife Polypropylene 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 tray (peach)Fiberglass 0 0 0 0 0 0 0 1 1 1 1 1 1 1 1 1 1 tray (tan) Stainless 0 0 11 1 1 1 1 1 1 1 1 1 1 1 1 1 steel slide 316 Suds No No No No No No No NoNo No No No No No No No No

Various surfactants demonstrated beneficial sheeting results under thetesting conditions. Surfactant type A, from table 6 demonstrated fullsheeting at relatively lower concentration than surfactant type D, I andJ. The surfactants were then advanced dynamic contact angle evaluationwith additional surfactants.

Example 3

Dynamic Contact Angle Measurement. The test quantitatively measured theangle at which a drop of solution contacts a test substrate. The rinseaid or surfactant(s) of desired concentration is created, and thenplaced into the apparatus. Rectangles of each plastic substrate material(melamine, polycarbonate, polypropylene) were cut from 6″×6″ squareslates. All experiments were carried out on a KRUSS DSA 100 drop shapeanalyzer. The solution and the coupon are then heated up in the chamberto the desired temperature. For each experiment, the rectangularsubstrate was placed onto the KRUSS DSA 100 stage with the temperaturecontrolled by a Peltier plate. The temperature was set to 80° C.

The substrate was allowed to rest on the stage for 10 minutes to allowit to reach the desired temperature. A 5 ul droplet of the surfactantsolution at 60 ppm surfactant concentration was deposited onto thesubstrate materials (polypropylene coupon, polycarbonate coupon and amelamine coupon), and the contact angle between the droplet and thesurface was measured over a period of 12 seconds. Three measurementswere carried out and averaged for each substrate/surfactant solutioncombination.

The deliverance of the drop to the substrate was recorded by a camera.The video captured by the camera is sent to a computer were the contactangle can be determined. The lower the contact angle the better thesolution will induce sheeting. This means that the dishware will drymore quickly and with fewer spots once it has been removed from the dishmachine.

The results showing contact angle measurement are shown in FIGS. 2-3were various surfactants were evaluated alone. FIGS. 2-3 demonstratethat as an individual surfactant A had the overall best performance forsheeting and wetting, with surfactant J, surfactant A2, and surfactant Bproviding good results as well. Surfactant D was selected as havingacceptable results based on the demonstrated defoaming. Based on theevaluation of dynamic contact angle measurement, the highest performingsurfactants were evaluated at differing ratios for foam (with andwithout a defoamer) as set forth in Example 4.

Example 4

The Glewwe foam evaluation set forth in Example 1 was conducted for thehighest performing surfactants of Example 3 and compared differingratios of the surfactants to evaluate for potential synergy of thecombinations of foaming benefits. Table 9 shows the combinations ofsurfactants screened for synergy.

Single surfactants or combinations with greater than 8″ of foam afterthe five minute initial reading are considered as excessive foam for theapplication. Single surfactants or combinations with less than 8″ offoam but greater than 5″ of foam after the five minute initial readingare considered as candidates for the application, but will needadditional defoaming from a separate source of a defoaming surfactantsuch as surfactant type D. Single surfactants or combinations with lessthan 5″ of foam after the five minute initial reading are consideredmore ideal candidates for the application if the resulting foamcontinues to break to less than 1″ after the final foam reading.Combinations of surfactant A and B, for example, would require additionof surfactant type D for favorable foam profiles.

TABLE 9 Rinse Aid After 1 min run After 5 (total) Temp grams Activestime (inches) minutes run time Run A I B D (° F.) used level Initial 15sec 1 min Initial 15 sec 1 min 1 0 0 1 0 140 0.15 100% 5 4½ 2 8¾ 8½ 8 20.45 0 0.4 0.15 140 0.15 100% 1 ⅛ Trace 5¼ 3 1½ 3 0 1 0 0 140 0.15 100%0 0 0 3 ¾ ½ 4 0 0.75 0 0.25 140 0.15 100% 0 0 0 4½ 3¼ 1½ 5 1 0 0 0 1400.15 100% 0 0 0 5 3½ 1½ 6 0.75 0 0 0.25 140 0.15 100% 0 0 0 2½ ½ ¼ 7 0 00.85 0.15 140 0.15 100% 2¾ 1¼ ⅛ 7½ 5 4½ 8 0.333 0.333 0.333 0 140 0.15100% ¼ 1/16 1/16 6¼ 5½ 2½ 9 1 0 0 0 140 0.15 100% 0 0 0 5⅛ 3⅝ 2⅝ 100.375 0.375 0 0.25 140 0.15 100% 0 0 0 2½ ¾ ⅜ 11 0.5 0 0.5 0 140 0.15100% 2 ½ ⅛ 9 9 9 12 0 0 0.75 0.25 140 0.15 100% 2 ½ ⅛ 6 4½ 2¼ 13 0 0.50.5 0 140 0.15 100% 1¼ ⅜ ⅛ 7¾ 6¾ 5⅜ 14 0 0.85 0 0.15 140 0.15 100% 0 0 02¼ ½ ⅜ 15 0.5 0.5 0 0 140 0.15 100% 0 0 0 3¼ 1 ¾ 16 0 0.425 0.425 0.15140 0.15 100% 1¼ ⅜ ¼ 5 2½ ¾ 17 0 0.375 0.375 0.25 140 0.15 100% ¾ ⅛ ⅛ 4¾1¼ ⅝ 18 0.361 0 0.388 0.25 140 0.15 100% 1 ¼ ⅛ 5¼ 2¾ ⅝ 19 0.437 0.412 00.15 140 0.15 100% 0 0 0 3 ¾ ½ 20 0.75 0 0 0.25 140 0.15 100% 0 0 0 3 ⅜¼

Table 10 shows combinations of surfactants initially screened forsynergy. Single surfactants or combinations with less than 5″ of foamafter the five minute initial reading are considered more idealcandidates for the application if the resulting foam continues to breakto less than 1″ after the final foam reading. Addition of surfactanttype D to combinations of surfactant A and I, for example, showfavorable foam profiles for the application.

TABLE 10 Rinse After 1 min run After 5 (total) Aid time (inches) minutesrun time Temp grams Actives 15 1 15 1 Product (° F.) used level Initialsec min Initial sec min A/I 80:20 Ratio 120 0.15 100% ½ ¼ ¼ 2½ ¾ ½ A/I80:20 Ratio 140 0.15 100% 0 0 0 3 ¾ ½ A/I 80:20 Ratio 160 0.15 100% 0 00 3 ¾ ½ #21 60% A/15% I/25% D 140 0.15 100% 0 0 0 2¾ ⅜ ⅜ #22 60% A/15%I/25% H 140 0.15 100% 0 0 0 2¾ ½ ⅜ #23 60% A/15% I/20% 140 0.15 100% 0 00 4½ 1 ½ D/5% H #24 60% A/15% I/20% 140 0.15 100% 0 0 0 3¾ 1 ⅜ D/5% B#25 56% A/14% I/25% 140 0.15 100% 0 0 0 3 ⅜ ⅜ D/5% B #26 60% A/15% 1400.15 100% 0 0 0 3½ 1 ⅜ I/20% H/5% D #27 56% A/14% 140 0.15 100% TraceTrace Trace 4 1½ ⅝ I/25% H/5% B

Table 11 shows further combinations of surfactants screened for synergywith beneficial results demonstrated with use of surfactant C in placeof surfactant B for a relatively lower foam combination. Whilesurfactant C, by itself do not exhibit acceptable foam characteristics,blend of surfactant A, I and C show favorable foam profile as opposed tosurfactant combinations of A, I and B. Single surfactants orcombinations with greater than 8″ of foam after the five minute initialreading are considered as excessive foam for the application. Singlesurfactants or combinations with less than 8″ of foam but greater than5″ of foam after the five minute initial reading are considered ascandidates for the application, but will need additional defoaming froma separate source of a defoaming surfactant such as surfactant type D,or alternatively the use of less surfactant type B in combination withadditional surfactant type C. Single surfactants or combinations withless than 5″ of foam after the five minute initial reading areconsidered more ideal candidates for the application if the resultingfoam continues to break to less than 1″ after the final foam reading.The combination of A, I and C meet favorable foam profiles while thecombination of A, I and B would require additional defoaming.

Example 5

The sheeting evaluation set forth in Example 2 was conducted using thehighest performing surfactants combinations of Example 4 comparingdiffering ratios of the surfactants to evaluate for potential synergy ofthe combinations of sheeting benefits with and without defoamer.

TABLE 12 (40% A/40% B/20% C; 0 grain; 65.5° C. (150° F.)) ppm, Activesin Rinse Aid 10 20 30 40 50 Glass tumbler 0 1 2 2 2 China Plate 0 0 1 12 Melamine Plate 0 1 1 2 2 Polypropylene Cup 0 0 1 1 2 (yellow) DinexBowl (blue) 0 0 1 1 2 Polypropylene Jug 0 0 1 1 2 (blue) PolysulfonateDish 0 0 1 1 2 (clear tan) Stainless Steel 0 0 1 1 2 Knife Polypropylenetray 0 0 1 1 2 (peach) Fiberglass tray (tan) 0 0 0 1 2 Stainless steelslide 0 1 1 2 2 316 Suds 0.25″ stable foam

The results depicted in Table 12 show an excellent result of thesurfactant system providing efficacy at low concentrations (50 ppm orless).

TABLE 13 (36.5% A/22.1% C/41.4% I; 0 grain; 64.4° C. (148° F.). ppm,Actives in Rinse Aid 10 20 30 40 50 60 70 80 90 100 Glass tumbler 0 0 00 0 1 1 1 2 2 China Plate 0 0 0 0 1 1 1 2 2 2 Melamine Plate 0 1 1 2 2 22 2 2 2 Polypropylene Cup 0 0 1 1 2 2 2 2 2 2 (yellow) Dinex Bowl (blue)0 1 1 1 2 2 2 2 2 2 Polypropylene Jug 0 1 1 1 1 1 2 2 2 2 (blue)Polysulfonate Dish 0 0 1 1 2 2 2 2 2 2 (clear tan) Stainless Steel Knife0 0 1 1 1 2 2 2 2 2 Polypropylene tray 0 0 1 1 1 1 1 1 1 2 (peach)Fiberglass tray (tan) 0 0 0 0 1 1 1 2 2 2 Stainless steel slide 0 1 1 11 1 1 1 2 2 316 Suds 0.125″ foam that breaks to trace within 15 seconds

The results depicted in Table 13 show improved results as compared tocommercial rinse additives with the surfactant system providing efficacyat concentrations at 100 ppm or less, with less foam than combinationsof A, B, C as observed during the test. However the combination of A, C,I does not provide the efficiency of complete sheeting as compared tothe combination of A, B, C.

TABLE 14 (40% A/20% C/40% A2; 0 grain, 66° C. (150° F.)). ppm, Activesin Rinse Aid 10 20 30 40 50 60 70 80 90 100 Glass tumbler 0 0 0 1 1 1 12 2 2 China Plate 0 0 1 1 1 1 1 1 1 2 Melamine Plate 1 1 1 1 1 2 2 2 2 2Polypropylene Cup 0 0 0 1 1 1 1 1 2 2 (yellow) Dinex Bowl (blue) 0 0 1 11 1 1 1 2 2 Polypropylene Jug 0 0 1 1 1 1 1 1 2 2 (blue) PolysulfonateDish 0 0 0 1 1 1 1 1 2 2 (clear tan) Stainless Steel Knife 0 0 0 1 1 1 11 2 2 Polypropylene tray 0 0 1 1 1 1 1 2 2 2 (peach) Fiberglass tray(tan) 0 0 0 0 1 1 1 1 1 2 Stainless steel slide 0 0 1 1 1 1 1 2 2 2 316Suds Trace of stable foam

The results depicted in Table 14 show improved results as compared tocommercial rinse additives with the surfactant system providing efficacyat concentrations at 100 ppm or less. The use of A with A2 and C doesnot provide the efficiency of complete sheeting as shown in examples ofsurfactant combinations of A, B and C.

TABLE 15 (40% A/20% B/40% A2; 0 grain; 66° C. (150° F.)). ppm, Activesin Rinse Aid 10 20 30 40 50 60 70 Glass tumbler 0 0 0 1 2 2 2 ChinaPlate 0 0 1 1 1 1 2 Melamine Plate 1 1 1 2 2 2 2 Polypropylene Cup 0 0 11 2 2 2 (yellow) Dinex Bowl (blue) 0 0 1 2 2 2 2 Polypropylene Jug 0 0 11 2 2 2 (blue) Polysulfonate Dish 0 0 1 2 2 2 2 (clear tan) StainlessSteel Knife 0 0 0 1 2 2 2 Polypropylene tray 0 0 1 2 2 2 2 (peach)Fiberglass tray (tan) 0 0 0 1 1 2 2 Stainless steel slide 0 1 1 1 2 2 2316 Suds Trace of stable foam

The results depicted in Table 15 show improved results as compared tocommercial rinse additives with the surfactant system providing efficacyat concentrations at 70 ppm or less. The use of A with A2 and B does notprovide the efficiency of complete sheeting as shown in examples ofsurfactant combinations of A, B and C.

TABLE 16 (56% A/5% B/14% 1/25% D; 0 grain; 63.3° C. (146° F.)). ppm,Actives in Rinse Aid 10 20 30 40 50 60 70 80 90 100 Glass tumbler 0 0 00 0 1 1 1 2 2 China Plate 0 0 1 1 1 1 1 1 1 2 Melamine Plate 1 1 1 1 1 12 2 2 2 Polypropylene Cup 0 0 0 0 1 2 2 2 2 2 (yellow) Dinex Bowl (blue)0 0 1 1 1 2 2 2 2 2 Polypropylene Jug 0 0 1 1 1 2 2 2 2 2 (blue)Polysulfonate Dish 0 0 0 1 1 1 1 2 2 2 (clear tan) Stainless Steel Knife0 0 0 0 1 1 1 1 2 2 Polypropylene tray 0 0 0 1 1 1 1 2 2 2 (peach)Fiberglass tray (tan) 0 0 0 0 1 1 1 1 1 2 Stainless steel slide 0 1 1 11 1 1 1 2 2 316 Suds Trace

The results depicted in Table 16 show improved results as compared tocommercial rinse additives with the surfactant system providing efficacyat concentrations at 100 ppm or less. However the addition of surfactanttypes I and D which exhibit favorable foam profiles individually,decrease the efficiency of complete sheeting.

TABLE 17 (40% J/40% A2/20% H; 0 grain; 64.4° C. (148° F.)). ppm, Activesin Rinse Aid 10 20 30 40 50 60 70 80 90 100 Glass tumbler 0 0 0 0 1 1 11 1 2 China Plate 0 0 0 0 0 0 1 1 2 2 Melamine Plate 1 1 1 1 2 2 2 2 2 2Polypropylene Cup 0 0 0 1 1 1 2 2 2 2 (yellow) Dinex Bowl (blue) 0 0 0 12 2 2 2 2 2 Polypropylene Jug 0 0 1 1 1 1 2 2 2 2 (blue) PolysulfonateDish 0 0 0 1 2 2 2 2 2 2 (clear tan) Stainless Steel Knife 0 0 0 1 1 1 12 2 2 Polypropylene tray 0 0 1 1 1 1 2 2 2 2 (peach) Fiberglass tray(tan) 0 0 1 1 1 1 1 2 2 2 Stainless steel slide 0 0 1 1 1 1 1 2 2 2 316Suds Trace gone within seconds

The results depicted in Table 17 show improved results as compared tocommercial rinse additives with the surfactant system providing efficacyat concentrations at 100 ppm or less. However the addition of surfactanttypes J and H which exhibit favorable foam profiles individually,decrease the efficiency of complete sheeting.

TABLE 18 (40% A/40% A2/20% H; 0 grain; 66° C. (150° F.)). ppm, Activesin Rinse Aid 10 20 30 40 50 60 70 80 90 Glass tumbler 0 0 0 0 1 1 1 2 1China Plate 0 0 0 0 1 1 1 1 2 Melamine Plate 1 1 1 1 1 1 2 2 2Polypropylene Cup 0 0 0 1 1 1 1 2 2 (yellow) Dinex Bowl (blue) 0 0 1 1 11 2 2 2 Polypropylene Jug 0 0 1 1 1 2 2 2 2 (blue) Polysulfonate Dish 00 1 1 1 2 2 2 2 (clear tan) Stainless Steel Knife 0 0 1 1 1 2 2 2 2Polypropylene tray 0 1 1 1 1 1 1 1 2 (peach) Fiberglass tray (tan) 0 1 11 1 1 1 2 2 Stainless steel slide 0 1 1 1 1 1 2 2 2 316 Suds No foam

The results depicted in Table 18 show improved results as compared tocommercial rinse additives with the surfactant system providing efficacyat concentrations at 100 ppm or less. However the addition of surfactanttypes G which exhibit favorable foam profiles individually, decrease theefficiency of complete sheeting as compared to blends of A, B, C.

TABLE 19 (50% B/50% D; 0 grain; 66° C. (150° F.)). ppm, Actives in RinseAid 10 20 30 40 50 60 70 Glass tumbler 0 0 0 1 2 2 2 China Plate 0 0 0 11 1 2 Melamine Plate 1 1 1 1 2 2 2 Polypropylene Cup 0 0 1 1 2 2 2(yellow) Dinex Bowl (blue) 0 0 1 1 2 2 2 Polypropylene Jug 0 0 0 1 2 2 2(blue) Polysulfonate Dish 0 0 1 1 2 2 2 (clear tan) Stainless SteelKnife 0 0 1 1 1 2 2 Polypropylene tray 0 1 1 1 2 2 2 (peach) Fiberglasstray (tan) 0 1 1 1 2 2 2 Stainless steel slide 316 0 0 1 1 1 2 2 Suds0.25″ stable foam

The results depicted in Table 19 show improved results as compared tocommercial rinse additives with the surfactant system providing efficacyat concentrations at 70 ppm or less. However, while the addition ofsurfactant combination of B with D provides unexpected efficiency, thecombination of B with D is not as efficient as the combination of A, B,C.

The results shown in Tables 12-19 show significantly improved andsynergistic results for surfactant system A/B/C (40/40/20 ratio), thesurfactant system A/B/A2 (40/20/40 ratio) and the surfactant system B/D(50/50 ratio). Unexpectedly, the synergistic combinations result in apotential antagonist effect with increased amount of defoamer in thesurfactant systems. Without being limited to a particular mechanism ofaction, the antagonist effect indicated by slightly worse efficacy withdefoamer may be a result of interfere with wetting and sheeting in thesurfactant systems according to the invention. As a result, thesurfactant systems and compositions employing the same preferably do notrequire a defoaming agent and/or employ a lesser concentration of adefoaming agent, including for example less than about 20 wt-% of adefoaming agent (such as surfactant D). In other embodiments, adetergent composition employing a defoaming agent may follow the use ofa surfactant system and compositions employing the same in anapplication of use.

The cumulative results shown in Tables 12-19 are also depicted in FIG. 4in chart format showing all sheeting data together. The graph isgenerated by apportioning a numerical value for the results of Tables12-19 (providing a total score or “sum” of the results). The steeper theline for each system indicates there was faster and complete sheetingachieved. The surfactant system A/B/C (40/40/20 ratio) is depicted asthe highest performer.

Example 6

These variations of surfactant systems tested in Example 5 were furtherevaluated using the dynamic contact angle as set forth in Example 3.FIGS. 5-7 show the contact angle versus time (dynamic contact) as donewith the sheeting study. The figures confirm the most preferredembodiment of the surfactant system is the surfactant system A/B/C(40/40/20 ratio).

Example 7

50 Cycle Redesposition Evaluation. The results of Examples 5-6 withpreferred surfactant systems were placed into two inline formulations atthe same surfactant level as the inline surfactant package. The inlineproducts were evaluated for performance versus the experimentalformulations in a 50 cycle test.

6 Glasses were placed in a rack in a diagonal line along with oneplastic glass. The machine was charged with 0.08% (800 ppm) detergentand the desired volume (mls) for each individual rinse aid. Thedetergent remained constant for each rinse aid evaluated. Aconcentration of 0.2% (2000 ppm) food soil was added to the machine(accounting for volume of sump). When the test started the detergent andrinse aid dispensers automatically dosed the proper amount each cycle.The detergent was controlled by conductivity and the rinse aid wasdispensed in milliliters per rack. The food soil was hand dosed for eachcycle to maintain 0.2% (2000 ppm) concentration. When the test wasfinished the glasses are allowed to dry overnight and evaluated for filmaccumulation. Glasses were then stained with coomassie blue to determineprotein residue.

The results are shown in FIGS. 8-9. FIG. 8 shows the average glass scoreand the plastic glass score, along with the change in results dependingon the placement of the glasses in the rack. The performance data showsthat the average glass score and the plastic score is much improvedusing the commercially available rinse aid with the surfactant systemA/B/C at the 40/40/20 ratio using the same surfactant percentage in boththe inline and the experimental formulations. Unexpectedly, theformulation is more effective at a 2 ml dose then the other formulas ata 4 ml dose, indicative of the synergy obtained from the combinationallowing dosing at lower actives level while provide at leastsubstantially similar performance, or as depicted in FIG. 8 havingimproved performance.

FIG. 9 shows the redeposition protein scores achieved using thepreferred surfactant system A/B/C at the 40/40/20 ratio used in thecommercial rinse aid A/B/C formulation, demonstrating improved resultson protein redeposition in comparison to the inline commercial rinseaid. Although the surfactant system provided for rinse aid benefits isnot alone responsible for protein removal, the sheeting of the rinse aidprevents redepositing on the ware from the soil load in the sump of thedishmachine demonstrating further benefit of the present invention.

Example 8

Variations of surfactants were evaluated specifically for hightemperature warewashing (80 C) according to embodiments of theinvention. Utilizings the methods described in Examples 1, 2 and 3,foam, sheeting and dynamic contact angle were determined respectively.Combinations of surfactants are described in Table 20.

TABLE 20 First Second Third Composition Composition CompositionSurfactant A 40 0 38 Surfactant A2 0 40 0 Surfactant B 40 40 38Surfactant C 20 20 0 Surfactant D 24

The results depicted in Table 21 show foam results by the methoddescribed in Example 1.

TABLE 21 Surfactant Combination (° F.) initial 15 sec 1 min initial 15sec 1 min A/B/C (40/40/20) 140 1½ ¾ ½ 5 2¼ 1¼ A2/B/C (40/40/20) 140 1½ ½½ 5 2 1⅜ A/B/D (38/38/24) 140 1 ¼ ⅛ 5½ 3½ ½

FIG. 10 is a summary of sheeting scores as a result of the methoddescribed in Example 2.

The results in Table 22 show a summary of contact angle as a result ofthe method described in Example 3. Exemplary contact angle is depictedat approximately 9 seconds after initial contact with the surface, using60 ppm active surfactant at 80 C.

TABLE 22 Mean Surfactant Time Combination (seconds) MelaminePolycarbonate Polypropylene A/B/C 9.10 17.00 36.30 44.10 (40/40/20)A2/B/C 9.06 15.20 34.87 40.45 (40/40/20) A/B/D 9.04 27.38 41.52 47.75(38/38/24)

Example 9

Variations of surfactants were evaluated specifically for lowtemperature warewashing (50 C) according to embodiments of theinvention. Utilizings the methods described in Examples 1, 2 and 3,foam, sheeting and dynamic contact angle were determined respectively.Combinations of surfactants are described in Table 23.

TABLE 23 First Second Third Fourth Composition Composition CompositionComposition Surfactant A 38 0 15 32 Surfactant A2 0 38 0 Surfactant B 3838 15 32 Surfactant C 0 0 0 16 Surfactant D 24 24 70 20

The results depicted in Table 24 show low temperature foam results bythe method described in Example 1.

TABLE 24 after 1 min run after 5 (total) time (inches) minutes run timeSurfactant Temp 1 1 Combination (° F.) initial 15 sec min initial 15 secmin A/B/D (38/38/24) 120 2 ¾ ½ 4 1½ ¾ A2/B/D (38/38/24) 120 1¾ ⅜ ½ 4 ½ ⅜A/B/D (15/15/70) 120 0 0 0 ¾ 0 0 A/B/C/D (32/32/16/20) 120 2.5 ¾ ¼ 6¾ 2¾¾

FIG. 11 is a summary of sheeting scores as a result of the methoddescribed in Example 2.

The results in Table 25 show a summary of contact angle as a result ofthe method described in example 3. Exemplary contact angle is depictedat approximately 9 seconds after initial contact with the surface, using60 ppm active surfactant at 50 C.

TABLE 25 Surfactant Mean Combination Time Melamine PolycarbonatePolypropylene A/B/D (38/38/24) 9.05 36.75 45.73 53.45 A2/B/D (38/38/24)9.04 34.20 44.08 57.57 A/B/D (15/15/70) 9.04 37.70 49.23 68.23 A/B/C/D(32/32/16/20) 9.04 24.94 38.26 48.60

Example 10

Further evaluation of surfactant combinations for solid formulationaccording to embodiments of the invention was conducted utilizing themethods described in Examples 1, 2 and 3 where foam, sheeting anddynamic contact angle were determined respectively. Combinations ofsurfactants are described in Table 26.

TABLE 26 Surfactant First Second Third Combination CompositionComposition Composition Surfactant A 25 30 30 Surfactant B 25 30 0Surfactant D 0 0 30 Surfactant G 50 40 40

The results depicted in Table 27 show low temperature foam results bythe method described in Example 1.

TABLE 27 after 1 min run after 5 (total) time (inches) minutes run timeSurfactant Temp 15 1 15 1 Combination (° F.) initial sec min initial secmin A/B/G (25/25/50) 140 3 1½ ¾ 9 8 7 A/B/G (30/30/40 140 1¾ ½ ¼ 6 4½ 2¼A/D/G (30/30/40 140 ½ > 1/16 > 1/16 3¼ ½ ¼

Table 28 is a summary of sheeting scores as a result of the methoddescribed in Example 2.

TABLE 28 (25% A/25% B/ 50% G; 0 grain; 66° C. (150° F.)). ppm, Activesin Rinse Aid 10 20 Glass tumbler 2 2 China Plate 2 2 Melamine Plate 2 2Polypropylene Cup 1 2 (yellow) Dinex Bowl (blue) 2 2 Polypropylene Jug 22 (blue) Polysulfonate Dish 2 2 (clear tan) Stainless Steel Knife 2 2Polypropylene tray 1 2 (peach) Fiberglass tray (tan) 2 2 Stainless steelslide 316 2 2 Suds 0.25″ stable foam

The results in Table 29 show a summary of contact angle as a result ofthe method described in Example 3. Exemplary contact angle is depictedat approximately 9 seconds after initial contact with the surface, using60 ppm active surfactant at 50° C.

TABLE 29 Surfactant Mean Combination Time Melamine PolycarbonatePolypropylene A/D/G (30/30/40) 9.04 35.3 45.4 54.9

Example 11

Further evaluation of surfactant systems was compared to Glassware,Flatware and Plate Ratings in commercial warewash applications comparedto commercially-available rinse aid controls. The objective of the trialwas to evaluate surfactant systems in comparison to positive controlsaimed to obtain equal (at lower actives) or better performance, asdetermined by ware ratings and dry times. The additional benefit ofreduced cost surfactant systems was also measured.

Rinse aid testing occurred at 10 distinct locations evenly split betweenhigh temperature (>180° F. rinse, hot water sanitizing) and lowtemperature (<180° F. rinse, chemical sanitizing) dish machines. Thepositive controls were each commercially-available rinse aids. Thefollowing information was collected during the 45 day baseline and 45day test phase: Glassware appearance ratings (overall, spot, film)(scale of 1 to 5) according to Table 30.

TABLE 30 Grade Spots Film Protein 1 No spots No film No Protein 2 RandomTrace amount of film. Light amount of amount of This is a barelyprotein. After dyeing spots. There perceptible amount of glass withCoomassie are spots but film that is barely blue reagent, the glass theycover less visible under intense is covered with a light than ¼ of thespot light conditions, amount of blue. A glass surface. but is notnoticeable trace amount of blue is if the glass is held up a grade of1.5. Protein to a florescent film is not readily light source. visibleto the eye unless dyed. 3 ¼ of the glass A slight of film is A mediumamount of surface is present. The glass protein film is present. coveredwith appears slightly filmed spots. when held up to a florescent lightsource. 4 ½ of the glass A moderate amount of A heavy amount of surfaceis film is present. The protein is present. covered with glass appearshazy spots when held up to a florescent light source. 5 The entire Aheavy amount of A very heavy amount surface of the filming is present.The of protein is present. A glass is coated glass appears cloudyCoomassie dyed glass with spots. when held up to a will appear darkblue. florescent light source.

The rinse aid delivery volumes were consistent at all locations. FIG. 12shows a scatterplot of the baseline (positive control) and test(surfactant system A/B/D 38/38/24). Beneficially, according to theresults of the testing, as shown in FIG. 12, the surfactant systemsaccording to the invention provided at least the same efficacy (atapproximately 50% lower actives) than the positive control.

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims. The above specification provides a description of themanufacture and use of the disclosed compositions and methods. Sincemany embodiments can be made without departing from the spirit and scopeof the invention, the invention resides in the claims.

1-26. (canceled)
 27. A rinse aid composition comprising: (A) asurfactant system comprising: a surfactant polymer having the formula:R⁷—O—(PO)y ₅(EO)x ₅(PO)y ₆  (D) wherein R⁷ is a branched C₈-C₁₆ Guerbetalcohol, x₅ is from 5 to 30, y₅ is from 1 to 4, and y₆ is from 10 to 20,and a surfactant polymer having the formula:

wherein x is from 88 to 108, y is from 57 to 77, and z is from 88 to108, and (B) at least one additional functional ingredient, wherein thefoam profile of the composition has a foam height of less than 5 inchesafter 5 minutes using the Glewwe method; and wherein the composition isplastic-compatible providing sheeting, wetting and drying properties.28. The composition of claim 27, wherein the surfactant polymers of thesurfactant system comprises from about 40 to about 60 parts by weight ofthe surfactant polymer (D) and from about 40 to about 60 parts by weightof the surfactant polymer (G).
 29. The composition of claim 27, whereinthe weight ratio of surfactant polymer (D) to surfactant polymer (G) inthe surfactant system is from about 60:40 to about 40:60.
 30. Thecomposition of claim 29, wherein the weight ratio of surfactant polymer(D) to surfactant polymer (G) in the surfactant system is about 50:50.31. The composition of claim 27, wherein the surfactant system furthercomprises at least one nonionic alcohol alkoxylate according to thefollowing formulas:R¹—O-(EO)_(x3)(PO)_(y3)—H  (A) wherein R¹ is a straight-chain C₁₀-C₁₆alkyl, wherein x₃ is from 5 to 8, and wherein y₃ is from 2 to 5, orR¹—O-(EO)_(x4)(PO)_(y4)—H  (A2) wherein R¹ is a straight-chain C₁₀-C₁₆alkyl, wherein x₄ is from 4 to 6, and wherein y₄ is from 3 to
 5. 32. Thecomposition of claim 31, wherein the weight ratio of surfactant polymer(A or A2) to surfactant polymer (G) to surfactant polymer (D) in thesurfactant system is about 30:30:40.
 33. The composition of claim 31,wherein the surfactant polymers of the surfactant system comprises fromabout 0 to about 60 parts by weight of the surfactant polymer (A or A2),from about 20 to about 80 parts by weight of the surfactant polymer (D),and from about 5 to about 70 parts by weight of the surfactant polymer(G).
 34. The composition of claim 27, wherein the composition is aliquid concentrate.
 35. The composition of claim 27, wherein thecomposition is a solid.
 36. The composition of claim 35, wherein thecomposition is a pressed or an extruded solid and optionally furthercomprises a block EO-PO-EO surfactant polymer.
 37. The composition ofclaim 27, wherein the contact angle of the composition is reduced atleast 5 degrees compared to a conventional rinse aid composition. 38.The composition of claim 27, wherein the additional functionalingredient is a hardening agent, carrier, chelating agent, sequesteringagent, builder, water conditioner, bleaching agent, sanitizer, defoamingagent, anti-redeposition agent, optical brightener, dye, odorant,stabilizing agent, dispersant, enzyme, corrosion inhibitor, thickenerand/or solubility modifier.
 39. The composition of claim 27, wherein ause solution thereof provides from about 1 ppm to about 50 ppmsurfactant system actives.
 40. The composition of claim 27, wherein thecomposition is a solid and comprises from about 10 wt-% to about 80 wt-%surfactant system, from about 10 wt-% to about 80 wt-% solidificationaid, from about 0 wt-% to about 10 wt-% water conditioning agent, fromabout 0 wt-% to about 10 wt-% chelant, from about 0 wt-% to about 20wt-% acidulant, from about 0 wt-% to about 5 wt-% water, and from about0 wt-% to about 2 wt-% preservative and/or dye.
 41. The composition ofclaim 27, wherein the composition is a liquid and comprises from about 2wt-% to about 90 wt-% surfactant system, from about 0 wt-% to about 20wt-% coupling agent, from about 0 wt-% to about 10 wt-% waterconditioning agent, from about 0 wt-% to about 10 wt-% chelant, fromabout 0 wt-% to about 15 wt-% acidulant, from about 0 wt-% to about 95wt-% water, and from about 0 wt-% to about 2 wt-% preservative and/ordye.
 42. A rinse aid composition comprising: (A) a surfactant systemcomprising: a surfactant polymer having the formula:R⁷—O—(PO)y ₅(EO)x ₅(PO)y ₆  (D) wherein R⁷ is a branched C₈-C₁₆ Guerbetalcohol, x₅ is from 5 to 30, y₅ is from 1 to 4, and y₆ is from 10 to 20,and a surfactant polymer having the formula:

wherein x is from 88 to 108, y is from 57 to 77, and z is from 88 to108, at least one nonionic alcohol alkoxylate according to the followingformulas:R¹—O-(EO)_(x3)(PO)_(y3)—H  (A) wherein R¹ is a straight-chain C₁₀-C₁₆alkyl, wherein x₃ is from 5 to 8, and wherein y₃ is from 2 to 5, orR¹—O-(EO)_(x4)(PO)_(y4)—H  (A2) wherein R¹ is a straight-chain C₁₀-C₁₆alkyl, wherein x₄ is from 4 to 6, and wherein y₄ is from 3 to 5, and (B)at least one additional functional ingredient, wherein the foam profileof the composition has a foam height of less than 5 inches after 5minutes using the Glewwe method; and wherein the composition isplastic-compatible providing sheeting, wetting and drying properties.43. The composition of claim 42, wherein the weight ratio of surfactantpolymer (A or A2) to surfactant polymer (G) to surfactant polymer (D) inthe surfactant system is about 30:30:40.
 44. A method for rinsing asurface comprising: (A) providing a rinse aid composition according toclaim 1; (B) contacting the composition with water to form a usesolution providing from about 1 ppm to about 125 ppm surfactant systemactives; and (C) applying the use solution to a surface in need ofrinsing at a temperature above 160° F., wherein the surfactant systemreduces the contact angle of the composition by at least about 5 degreescompared to the contact angle of a commercially-available rinse aidcomposition to induce sheeting and result in a faster drying time of thesurface.
 45. The method of claim 44, wherein the surfactant systemreduces the contact angle of the composition by at least about 10degrees compared to the contact angle of a commercially-available rinseaid to induce sheeting and result in a faster drying time of thesurface.
 46. The method of claim 44, wherein the surface is a ware. 47.The method of claim 46, wherein the ware is plastic.
 48. The method ofclaim 44, wherein the ware dries within about 30 to about 90 secondsafter the use solution is applied to the ware.
 49. The method of claim44, wherein the method takes place in a consumer or institutional dishmachine.